Crash Course on Batteries

When was the Battery Invented?

One of the most remarkable and novel discoveries in the last 400 years was electricity. We might ask, Has electricity been around that long? The answer is yes, and perhaps much longer, but its practical use has only been at our disposal since the mid to late 1800s, and in a limited way at first. One of the earliest public works gaining attention was enlightening the 1893 Chicagos World Columbia Exposition with 250,000 light bulbs, and illuminating a bridge over the river Seine during the 1900 World Fair in Paris. The use of electricity may go back further. While constructing a railway in 1936 near Baghdad, workers uncovered what appeared to be a prehistoric battery, also known as the Parthian Battery. The object dates back to the Parthian period and is believed to be 2,000 years old. The battery consisted of a clay jar that was filled with a vinegar solution into which an iron rod surrounded by a copper cylinder was inserted. This device produced 1.1 to 2.0 volts of electricity. Figure 1 illustrates the Parthian Battery.

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Figure 1: Parthian Battery. A clay jar of a prehistoric battery holds an iron rod surrounded by a copper cylinder. When filled with vinegar or electrolytic solution, the jar produces 1.1 to 2 volts. Not all scientists accept the Parthian Battery as a source of energy. It is possible that the device was used for electroplating, such as adding a layer of gold or other precious metals to a surface. The Egyptians are said to have electroplated antimony onto copper over 4,300 years ago. Archeological evidence suggests the Babylonians were the first to discover and employ a galvanic technique in the manufacturing of jewelry by using an electrolyte based on grape juice to gold plate stoneware. The Parthians, who ruled Baghdad (ca. 250 BC), may have used batteries to electroplate silver. One of the earliest methods to generate electricity in modern times was through creating a static charge. In 1660, Otto von Guericke constructed an electrical machine using a large sulfur globe which, when rubbed and turned, attracted feathers and small pieces of paper. Guericke was able to prove that the sparks generated were electrical in nature. The first practical use of static electricity was the electric pistol, which Alessandro Volta (1745 1827) invented. He thought of providing long-distance communications, albeit only one Boolean bit. An iron wire supported by wooden poles was to be strung from Como to Milan, Italy. At the receiving end, the wire would terminate in a jar filled with methane gas. To signal a coded

event, an electrical spark would be sent by wire for the purpose of detonating the electric pistol. This communications link was never built. Figure 1-2 shows a pencil rendering of Alessandro Volta.

Figure 2: Alessandro Volta, inventor of the electric battery Voltas discovery of the decomposition of water by an electrical current laid the foundation of electrochemistry. Courtesy of Cadex

In 1791, while working at Bologna University, Luigi Galvani discovered that the muscle of a frog would contract when touched by a metallic object. This phenomenon became known as animal electricity. Prompted by these experiments, Volta initiated a series of experiments using zinc, lead, tin and iron as positive plates (cathode); and copper, silver, gold and graphite as negative plates (anode). The interest in galvanic electricity soon became widespread.

Early Batteries
Volta discovered in 1800 that certain fluids would generate a continuous flow of electrical power when used as a conductor. This discovery led to the invention of the first voltaic cell, more commonly known as the battery. Volta discovered further that the voltage would increase when voltaic cells were stacked on top of each other. Figure 3 illustrates such a serial connection.

Figure 1-3: Four variations of Voltas electric battery Metals in a battery have different electrical effects. Volta noticed that the voltage potential with dissimilar substances got stronger the farther apart they were from one another. The first number in the metals listed below is the affinity to attract electrons; the second is the standard potential from the first

oxidation state. Zinc = 1.6 / -0.76 V Lead = 1.9 / -0.13 V Tin = 1.8 / -1.07 V Iron = 1.8 / -0.04 V Copper = 1.9 / 0.159 V Silver = 1.9 / 1.98 V Gold = 2.4 / 1.83 V Carbon = 2.5 / 0.13 V The metals determine the battery voltage; they were separated with moist paper soaked in salt water. Courtesy of Cadex
In the same year, Volta released his discovery of a continuous source of electricity to the Royal Society of London. No longer were experiments limited to a brief display of sparks that lasted a fraction of a second. An endless stream of electric current now seemed possible. France was one of the first nations to officially recognize Voltas discoveries. This was during a time when France was approaching the height of scientific advancements and new ideas were welcomed with open arms, helping to support of the countrys political agenda. By invitation, Volta addressed the Institute of France in a series of lectures at which Napoleon Bonaparte was present as a member of the institute (see Figure 4).

Figure 4: Voltas experimentations at the Institute of France Voltas discoveries so impressed the world that in November 1800 the French National Institute invited him to lectures at events in which Napoleon Bonaparte participated. Napoleon helped with the experiments, drawing sparks from the battery, melting a steel wire, discharging an electric pistol and decomposing water into its elements. Courtesy of Cadex In 1800, Sir Humphry Davy, inventor of the miners safety lamp, began testing the chemical effects of electricity and found out that decomposition occurred when passing electrical current through substances. This process was later called electrolysis. He made new discoveries by installing the worlds largest and most powerful electric battery in the vaults of the Royal Institution of London. Connecting the battery to charcoal electrodes produced the first electric light. Witnesses reported that his voltaic arc lamp produced the most brilliant ascending arch of light ever seen. In 1802, William Cruickshank designed the first electric battery for mass production. Cruickshank arranged square sheets of copper with equal-sized sheets sizes of zinc. These sheets were placed into a long rectangular wooden box and soldered together. Grooves in the box held the metal plates in position, and the sealed box was then filled with an electrolyte of brine, or a watered-down acid. This resembled the flooded battery that is still with us today. Figure 5 illustrates the battery workshop of Cruickshank.

Figure 5: Cruickshank and the first flooded battery. William Cruickshank, an English chemist, built a battery of electric cells by joining zinc and copper plates in a wooden box filled with an electrolyte solution. This flooded design had the advantage of not drying out with use and provided more energy than Voltas disc arrangement. Courtesy of Cadex

Invention of the Rechargeable Battery

In 1836, John F. Daniell, an English chemist, developed an improved battery that produced a steadier current than earlier devices. Until this time, all batteries were primary, meaning they could not be recharged. In 1859, the French physicist Gaston Plant invented the first rechargeable battery. It was based on lead acid, a system that is still used today. In 1899, Waldmar Jungner from Sweden invented the nickel-cadmium battery (NiCd), which used nickel for the positive electrode (cathode) and cadmium for the negative (anode). High material costs compared to lead acid limited its use and two years later, Thomas Edison produced an alternative design by replacing cadmium with iron. Low specific energy, poor performance at low temperature and high self-discharge limited the success of the nickel-iron battery. It was not until 1932 that Shlecht and Ackermann achieved higher load currents and improved the longevity of NiCd by inventing the sintered pole plate. In 1947, Georg Neumann succeeded in sealing the cell. For many years, NiCd was the only rechargeable battery for portable applications. In the 1990s, environmentalists in Europe became concerned about environmental contamination if NiCd were carelessly disposed; they began to restrict this chemistry and asked the consumer industry to switch to Nickel-metal-hydride (NiMH), an environmentally friendlier battery. NiMH is similar

to NiCd, and many predict that NiMH will be the stepping-stone to the more enduring lithium-ion (Li-ion). Most research activities today revolve around improving lithium-based systems. Besides powering cellular phones, laptops, digital cameras, power tools and medical devices, Li-ion is also used for electric vehicles. The battery has a number of benefits, most notably its high specific energy, simple charging, low maintenance and being environmentally benign.

Electricity Through Magnetism

The discovery of how to generate electricity through magnetism came relatively late. In 1820, Andr-Marie Ampre (17751836) noticed that wires carrying an electric current were at times attracted to and at other times repelled from one another. In 1831, Michael Faraday (1791 1867) demonstrated how a copper disc provided a constant flow of electricity while revolving in a strong magnetic field. Faraday, assisting Davy and his research team, succeeded in generating an endless electrical force as long as the movement between a coil and magnet continued. This led to the invention of the electric generator, and reversing the process enabled the electric motor. Shortly thereafter, transformers were developed that converted alternating current (AC) to any desired voltage. In 1833, Faraday established the foundation of electrochemistry on which Faradays law is based. Faradays law of induction relates to electromagnetism linked to transformers, inductors, and many types of electrical motors and generators. Once the relationship with magnetism was understood, large generators began producing a steady flow of electricity. Motors followed that enabled mechanical movement, and the Edison light bulb appeared to conquer darkness. After George Westinghouse lit up Chicago's World Columbian Exposition in 1893, Westinghouse built three large generators to transform energy from the Niagara Falls to electricity. The three-phase AC technology developed by Nikola Tesla enabled transmission lines to carry electric power over great distances. Electricity was thus made widely available to humanity to improve the quality of life.

Figure 6: 250,000 light bulbs illuminate Chicago's World Columbian Exposition in 1896. The success of the electric light led to building three large hydro generators at Niagara Falls. Courtesy of the Brooklyn Museum Archives. Goodyear Archival Collection The invention of the electronic vacuum tube in the early 1900s formed the significant next step towards high technology, enabling frequency oscillators, signal amplifications and digital

switching. This led to radio broadcasting in the 1920s and the first digital computer, called ENIAC, in 1946. The discovery of the transistor in 1947 paved the way for the arrival of the integrated circuit 10 years later, and the microprocessor ushered in the Information Age, forever changing the way we live and work. Humanity depends on electricity, and with increased mobility people have gravitated more and more towards portable power first for wheeled applications, then portability and finally wearable use. As awkward and unreliable as the early batteries may have been, future generations may look at todays technologies as nothing more than clumsy experiments.

Battery Developments
Inventions in the 1700s and 1800s are well documented and credit goes to the dignified inventors. Benjamin Franklin invented the Franklin stove, bifocal eyeglasses and the lightning rod. He was unequaled in American history as an inventor until Thomas Edison emerged. Edison was a good businessman who may have taken credit for inventions others had made. Contrary to popular belief, Edison did not invent the light bulb; he improved upon a 50-year-old idea by using a small, carbonized filament lit up in a better vacuum. Although a number of people had worked on this idea before, Edison gained the financial reward by making the concept commercially viable to the public. The phonograph is another success story for which Edison received due credit. Countries often credit their own citizens for having made important inventions, whether or not they deserve it. When visiting museums in Europe, the USA and Japan one sees such bestowment. The work to develop the car, x-ray machines, telephones, broadcast radio, televisions and computers might have been done in parallel, not knowing of others advancements at that time, and the rightful inventor is often not clearly identified. Similar uncertainties exist with the invention of new battery systems, and we give respect to research teams and organizations rather than individuals. Table 1 summarizes battery advancements and lists inventors when available.

Year

Inventor William Gilbert (UK) Luigi Galvani (Italy) Alessandro Volta (Italy) William Cruickshank (UK) Andr-Marie Ampre (France) Michael Faraday (UK) John F. Daniell (UK) William Robert Grove (UK) Gaston Plant (France) Georges Leclanch (France) Waldmar Jungner (Sweden) Thomas A. Edison (USA) Shlecht & Ackermann (D)

Activity Establishment of electrochemistry study Discovery of animal electricity Invention of the voltaic cell (zinc, copper disks) First electric battery capable of mass production Electricity through magnetism Announcement of Faradays law Invention of the Daniell cell Invention of the fuel cell (H2/O2) Invention of the lead acid battery Invention of the Leclanch cell (carbon-zinc) Invention of the nickel-cadmium battery Invention of the nickel-iron battery Invention of the sintered pole plate

1600
1791 1800 1802 1820 1833 1836 1839 1859 1868 1899 1901 1932

1947 1949 1970s 1990 1991 1994 1996 1996 2002

Georg Neumann (Germany) Lew Urry, Eveready Battery Group effort Group effort Sony (Japan) Bellcore (USA) Moli Energy (Canada) University of Texas (USA) University of Montreal, Quebec Hydro, MIT, others

Successfully sealing the nickel-cadmium battery Invention of the alkaline-manganese battery Development of valve-regulated lead acid battery Commercialization of nickel-metal-hydride battery Commercialization of lithium-ion battery Commercialization of lithium-ion polymer Introduction of Li-ion with manganese cathode Identification of Li-phosphate (LiFePO4) Improvement of Li-phosphate, nanotechnology, commercialization

Table 1: History of modern battery development. No new major battery system has entered the commercial market since the invention of Li-phosphate in 1996.

Battery Developments
Inventions in the 1700s and 1800s are well documented and credit goes to the dignified inventors. Benjamin Franklin invented the Franklin stove, bifocal eyeglasses and the lightning rod. He was unequaled in American history as an inventor until Thomas Edison emerged. Edison was a good businessman who may have taken credit for inventions others had made. Contrary to popular belief, Edison did not invent the light bulb; he improved upon a 50-year-old idea by using a small, carbonized filament lit up in a better vacuum. Although a number of people had worked on this idea before, Edison gained the financial reward by making the concept commercially viable to the public. The phonograph is another success story for which Edison received due credit. Countries often credit their own citizens for having made important inventions, whether or not they deserve it. When visiting museums in Europe, the USA and Japan one sees such bestowment. The work to develop the car, x-ray machines, telephones, broadcast radio, televisions and computers might have been done in parallel, not knowing of others advancements at that time, and the rightful inventor is often not clearly identified. Similar uncertainties exist with the invention of new battery systems, and we give respect to research teams and organizations rather than individuals. Table 1 summarizes battery advancements and lists inventors when available.

Year 1600 1791 1800

Inventor William Gilbert (UK) Luigi Galvani (Italy) Alessandro Volta (Italy)

Activity Establishment of electrochemistry study Discovery of animal electricity Invention of the voltaic cell (zinc, copper

1802 1820 1833

William Cruickshank (UK) Andr-Marie Ampre (France) Michael Faraday (UK)

disks) First electric battery capable of mass production Electricity through magnetism Announcement of Faradays law Invention of the Daniell cell Invention of the fuel cell (H2/O2) Invention of the lead acid battery Invention of the Leclanch cell (carbon-zinc) Invention of the nickel-cadmium battery Invention of the nickel-iron battery

1836 John F. Daniell (UK) 1839 William Robert Grove (UK) 1859 Gaston Plant (France) 1868 Georges Leclanch (France) 1899 Waldmar Jungner (Sweden)

1901 1932 1947 1949 1970s 1990 1991 1994 1996 1996

Thomas A. Edison (USA) Shlecht & Ackermann (D) Georg Neumann (Germany)

Invention of the sintered pole plate Successfully sealing the nickel-cadmium battery Invention of the alkaline-manganese battery

Lew Urry, Eveready Battery Group effort Group effort Sony (Japan) Commercialization of lithium-ion battery Bellcore (USA) Commercialization of lithium-ion polymer Moli Energy (Canada) University of Texas (USA) Introduction of Li-ion with manganese cathode Identification of Li-phosphate (LiFePO4) Development of valve-regulated lead acid battery Commercialization of nickel-metal-hydride battery

2002

University of Montreal, Quebec Hydro, MIT, others

Improvement of Li-phosphate, nanotechnology, commercialization

Table 1: History of modern battery development. No new major battery system has entered the commercial market since the invention of Li-phosphate in 1996.

Global Battery Markets

The battery market is expanding, and the global revenue in 2009 was a whopping $47.5 billion.* With the growing demand for portable electronics and the desire to connect and work outside the confines of four walls, experts predict that this figure will reach $74 billion in 2015. These numbers are speculative and include batteries for the electric powertrain of cars.

An Overview of Battery Types

Batteries are divided into two categories: primary and secondary. In 2009, primary batteries made up 23.6 percent of the global market. Frost & Sullivan (2009) predict a 7.4 percent decline of the primary battery in revenue distribution by 2015. Primary batteries are used in watches, electronic keys, remote controls, childrens toys, light beacons and military devices. The real growth lies in secondary batteries. Frost & Sullivansay that rechargeable batteriesaccount for 76.4 percent of the global market, a number that is expected to increase to 82.6 percent in 2015. Batteries are also classified by chemistry and the most common are lithium-, lead-, and nickel-based systems. Figure 1 illustrates the distribution of these chemistries.

Figure 1: Revenue contributions by different battery chemistries Courtesy of Frost & Sullivan (2009) Lithium-ion is the battery of choice for consumer products, and no other systems threaten to interfere with its dominance at this time. The lead acid market is similar in

size to Li-ion. Here the applications are divided into SLI (starter battery) for automotive, stationary for power backup, and deep-cycle for wheeled mobility such as golf cars, wheelchairs and scissor lifts. Lead acid holds a solid position, as it has done for the last hundred years. There are no other systems that threaten to unseat this forgiving and low-cost chemistry any time soon. High specific energy and long storage has made alkaline more popular than carbon-zinc, which Georges Leclanch invented in 1868. The environmentally benign nickel-metalhydride (NiMH) continues to hold an important role, as it replaces many applications previously served by nickel-cadmium (NiCd). However, at only three percent market share, NiMH is a minor player in the battery world and will likely relinquish more of its market to Li-ion by 2015. Developing nations will contribute to future battery sales, and new markets are the electric bicycle in Asia and storage batteries to supply electric power to remote communities in Africa and other parts of the world. Wind turbines, solar power and other renewable sources also use storage batteries for load leveling. The large grid storage batteries used for load leveling collect surplus energy from renewable resources during high activity and supply extra power on heavy user demand. Read more about Batteries for Stationary, Grid Storage. A major new battery user might be the electric powertrain for personal cars. However, battery cost and longevity will dictate how quickly the automotive sector will adopt this new propulsion system. Energy from oil is cheap, convenient and readily available; any alternative faces difficult challenges. Government incentives may be provided, but such intervention distorts the true cost of energy, shields the underlying problem with fossil fuel and only satisfies certain lobby groups through short-term solutions. During the last five years or so, no new battery system has emerged that can claim to offer disruptive technology. Although much research is being done, no new concept is ready to enter the market at the time of writing, nor are new developments close to breakthrough point. There are many reasons for this apparent lack of progress: few products have requirements that are as stringent as the battery. For example, battery users want low price, long life, high specific energy, safe operation and minimal maintenance. In addition, the battery must work at hot and cold temperatures, deliver high power on demand and charge quickly. Only some of these attributes are achievable with various battery technologies. Most consumers are satisfied with the battery performance on portable devices. Todays battery technology also serves power backup and wheeled mobility reasonably well. Using our current battery technology for electric powertrains on cars, however, might prove difficult because the long-term effects in that environment are not fully understood. The switch to a power source offering a fraction of the kinetic energy compared to fossil fuels will be an eye-opener for motorists who continually demand larger vehicles with more. Read more about the Cost of Power.

Advancements in Batteries
Batteries advance on two fronts, and these developments reflect themselves in increased specific energy for longer runtimes and improved specific power for good

power delivery on demand. Figure 2 illustrates the energy and power densities of lead acid, nickel-cadmium (NiCd), nickel-metal-hydride (NiMH) and the Li-ion family (Liion).

Figure 1-8: Specific energy and specific power of rechargeable batteries. Specific energy is the capacity a battery can hold in watt-hours per kilogram (Wh/kg); specific power is the batterys ability to deliver power in watts per kilogram (W/kg). Rechargeable lithium-metal batteries (Li-metal) were introduced in the 1980s, but instability with metallic lithium on the anode prompted a recall in 1991. Its high specific energy and good power density are challenging manufacturers revisit into this powerful chemistry again. Enhanced safety may be possible by mixing metallic lithium with tin and silicon. Experimental Li-metal batteries achieve 300Wh/kg, a specific energy that is of special interest to the electric vehicle. Read more about Experimental Rechargeable Batteries.

* All references to dollar ($) pricing are in US dollars at the time of writing.

Getting to Know the Battery

The battery dictates the speed with which mobility advances. So important is this portable energy source that any incremental improvement opens new doors for many products. The better the battery, the greater our liberty will become.

Besides packing more energy into the battery, engineers have also made strides in reducing power consumption of portable equipment. These advancements go hand-inhand with longer runtimes but are often counteracted by the demand for additional features and more power. The end result is similar runtimes but enhanced performance. The battery has not advanced at the same speed as microelectronics, and the industry has only gained 8 to 10 percent in capacity per year during the last two decades. This is a far cry from Moores Law* that specifies a doubling of the number of transistors in an integrated circuit every two years. Instead of two years, the capacity of lithium-ion took 10 years to double. In parallel with achieving capacity gain, battery makers must also focus on improving manufacturing methods to ensure better safety. The recent recall of millions of lithiumcobalt packs caused by thermal runaway is a reminder of the inherent risk in condensing too much energy into a small package. Better manufacturing practices should make such recalls a thing of the past. A generation of Li-ion batteries is emerging that are built for longevity. These batteries have a lower specific energy (capacity) than those for portable electronics and are increasingly being considered for the electric powertrain of vehicles. People want an inexhaustible pool of energy in a package that is small, cheap, safe and clean, and the battery industry can only fulfill this desire partially. As long as the battery is an electrochemical process, there will be limitations on capacity and life span. Only a revolutionary new storage system could satisfy the unquenchable thirst for mobile power, and its anyones guess whether this will be lithium-air, the fuel cell, or some other ground-breaking new power generator, such as atomic fusion. For most of us, the big break might not come in our lifetime.

Meeting Expectations
Many battery novices argue, wrongly, that all advanced battery systems offer high energy densities, deliver thousands of charge/discharge cycles and come in a small size. While some of these attributes are possible, this is not attainable in one and the same battery in a given chemistry. A battery may be designed for high specific energy and small size, but the cycle life is short. Another battery may be built for high load capabilities and durability, and the cells are bulky and heavy. A third pack may have high capacity and long service life, but the manufacturing cost is out of reach for the average consumer. Battery manufacturers are well aware of customer needs and respond by offering products that best suit the application intended. The mobile phone industry is an example of this clever adaptation. The emphasis is on small size, high energy density and low price. Longevity is less important here. The terms nickel-metal-hydride (NiMH) and lithium-ion (Li-ion) do not automatically mean high specific energy. For example, NiMH for the electric powertrain in vehicles has a specific energy of only 45Wh/kg, a value that is not much higher than lead acid. The consumer NiMH, in comparison, has about 90Wh/kg. The Li-ion battery for hybrid and electric vehicles can have a specific energy as low as 60Wh/kg, a value that is

comparable with nickel-cadmium. Li-ion for cell phones and laptops, on the other hand, has two to three times this specific energy. The Cadex-sponsored website www.BatteryUniversity.com generates many interesting questions. Those that stand out are, Whats the best battery for a remote-controlled car, a portable solar station, an electric bicycle or electric car? There is no universal battery that fits all needs and each application is unique. Although lithium-ion would in most instances be the preferred choice, high price and the need for an approved protection circuit exclude this system from use by many hobbyists and small manufacturers. Removing Li-ion leads back to the nickel- and lead-based options. Consumer products may have benefited the most from battery advancements. High volume made Li-ion relatively inexpensive. Will the battery replace the internal combustion engine of cars? It may come as a surprise to many that we dont yet have an economical battery that allows long-distance driving and lasts as long as the car. Batteries work reasonably well for portable applications such as cell phones, laptops and digital cameras. Low power enables an economical price; the relative short battery life is acceptable in consumer products; and we can live with a decreasing runtime. While the fading capacity can be annoying, it does not endanger safety. As we examine the characteristics of battery systems and compare alternative power sources, such as the fuel cell and the internal combustion (IC) engine, we realize that the battery is best suited for portable and stationary systems. For motive applications such as trains, ocean going ships and aircraft, the battery lacks capacity, endurance and reliability. The dividing line, in my opinion, lies with the electric vehicle.

* In 1965, Gordon Moore said that the number of transistors in an integrated circuit would double every two years. The prediction became true and is being carried into the 21st century. Applied to a battery, Moores Law would shrink a starter battery in a car to the size of a coin.

Comparing the Battery with other Power Sources

This article begins with the positive traits of the battery, and then moves into the limitations when compared with other power sources.

Energy storage
Batteries store energy well and for a considerable length of time. Primary batteries (nonrechargeable) hold more energy than secondary (rechargeable), and the self-discharge is lower. Alkaline cells are good for 10 years with minimal losses. Lead-, nickel- and lithium-based batteries need periodic recharges to compensate for lost power.

Specific energy (Capacity)

A battery may hold adequate energy for portable use, but this does not transfer equally well for large mobile and stationary systems. For example, a 100kg (220lb) battery produces about 10kWh of energy an IC engine of the same weight generates 100kW.

Responsiveness
Batteries have a huge advantage over other power sources in being ready to deliver on short notice think of the quick action of the camera flash! There is no warm-up, as is the case with the internal combustion (IC) engine; the power from the battery flows within a fraction of a second. In comparison, a jet engine takes several seconds to gain power, a fuel cell requires a few minutes, and the cold steam engine of a locomotive needs hours to build up steam.

Power bandwidth
Rechargeable batteries have a wide power bandwidth, a quality that is shared with the diesel engine. In comparison, the bandwidth of the fuel cell is narrow and works best within a specific load. Jet engines also have a limited power bandwidth. They have poor low-end torque and operate most efficiently at a defined revolution-per-minute (RPM).

Environment
The battery runs clean and stays reasonably cool. Sealed cells have no exhaust, are quiet and do not vibrate. This is in sharp contrast with the IC engine and larger fuel cells that require noisy compressors and cooling fans. The IC engine also needs air and exhausts toxic gases.

Efficiency
The battery is highly efficient. Below 70 percent charge, the charge efficiency is close to 100 percent and the discharge losses are only a few percent. In comparison, the energy efficiency of the fuel cell is 20 to 60 percent, and the thermal engines is 25 to 30 percent. (At optimal air intake speed and temperature, the GE90-115 on the Boeing 777 jetliner is 37 percent efficient.)

Installation
The sealed battery operates in any position and offers good shock and vibration tolerance. This benefit does not transfer to the flooded batteries that must be installed in the upright position. Most IC engines must also be positioned in the upright position and mounted on shock- absorbing dampers to reduce vibration. Thermal engines also need air and an exhaust.

Operating cost
Lithium- and nickel-based batteries are best suited for portable devices; lead acid batteries are economical for wheeled mobility and stationary applications. Cost and weight make batteries impractical for electric powertrains in larger vehicles. The price of a 1,000-watt battery (1kW) is roughly $1,000 and it has a life span of about 2,500 hours. Adding the replacement cost of $0.40/h and an average of $0.10/kWh for charging, the cost per kWh comes to about $0.50. The IC engine costs less to build per watt and lasts for about 4,000 hours. This brings the cost per 1kWh to about $0.34. Read more about the Battery Against Fossil Fuel.

Maintenance
With the exception of watering of flooded lead batteries and discharging NiCds to prevent memory, rechargeable batteries require low maintenance. Service includes cleaning of corrosion buildup on the outside terminals and applying periodic performance checks.

Service life
The rechargeable battery has a relatively short service life and ages even if not in use. In consumer products, the 3- to 5-year lifespan is satisfactory. This is not acceptable for larger batteries in industry, and makers of the hybrid and electric vehicles guarantee their batteries for 8 to 10 years. The fuel cell delivers 2,000 to 5,000 hours of service and, depending on temperature, large stationary batteries are good for 5 to 20 years.

Temperature extremes
Like molasses, cold temperatures slow the electrochemical reaction and batteries do not perform well below freezing. The fuel cell shares the same problem, but the internal combustion engine does well once warmed up. Charging must always be done above freezing. Operating at a high temperature provides a performance boost but this causes rapid aging due to added stress. Read about Discharging at High and Low Temperatures.

Charge time
Here, the battery has an undisputed disadvantage. Lithium- and nickel-based systems take 1 to 3 hours to charge; lead acid typically takes 14 hours. In comparison, filling up a vehicle only takes a few minutes. Although some electric vehicles can be charged to 80 percent in less than one hour on a high-power outlet, users of electric vehicles will need to make adjustments.

Disposal
Nickel-cadmium and lead acid batteries contain hazardous material and cannot be disposed of in landfills. Nickel-metal-hydrate and lithium systems are environmentally

friendly and can be disposed of with regular household items in small quantities. Authorities recommend that all batteries be recycled.

Battery Definitions
Batteries come in all shapes and sizes and there could be as many types as there are species of dog. Rather than giving batteries unique names as we do with pets, we distinguish batteries by chemistry, voltage, size, specific energy (capacity), specific power, (delivery of power) and more. A battery can operate as a single cell to power a cellular phone, or be connected in series to deliver several hundred volts to serve a UPS (uninterruptible power supply system) and the electric powertrain of a vehicle. Some batteries have high capacity but cannot deliver much power, while a starter battery has a relatively low capacity but can crank the engine with 300A. The largest battery systems are used for grid storage to store and delivery energy derived from renewable power sources such as wind turbines and solar systems. A 30megawatt (MW) wind farm uses a storage battery of about 15MW. This is the equivalent of 20,000 starter batteries and costs about $10 million. One mega-watt feeds 50 houses or a super Walmart store. Lets now examine each of the battery characteristics further.

Chemistry
The most common chemistries are lead, nickel and lithium. Each system requires its own charging algorithm. Unless provisions are made to change the charge setting, different battery chemistries cannot be interchanged in the same charger. Also observe the chemistry when shipping and disposing of batteries; each type has a different regulatory requirement.

Voltage
Voltage describes the nominal open circuit voltage (OCV), which varies with chemistry and number of cells connected in series. Always observe the correct voltage when connecting to a load or a charger. Do not proceed if the voltage does not agree.

Capacity
Capacity represents the specific energy in ampere-hours (Ah). Manufacturers often overrate a battery by giving a higher Ah rating than it can provide. You can use a battery with different Ah (but correct voltage), provided the rating is high enough. Chargers have some tolerance to batteries with different Ah ratings. A larger battery will take longer to charge than a small one.

Cold cranking amps (CCA)

CCA specifies the ability to draw high load current at 18C (0F) on starter batteries. Different norms specify dissimilar load durations and end voltages.

Specific energy and energy density

Specific energy or gravimetric energy density defines the battery capacity in weight (Wh/kg); energy density or volumetric energy density is given in size (Wh/l). A battery can have a high specific energy but poor specific power (load capability), as is the case in an alkaline battery. Alternatively, a battery may have a low specific energy but can deliver high specific power, as is possible with the supercapacitor. Specific energy is synonymous with battery capacity and runtime.

Specific power
Specific power or gravimetric power density indicates the loading capability, or the amount of current the battery can provide. Batteries for power tools exhibit high specific power but have reduced specific energy (capacity). Specific power is synonymous with low internal resistance and the delivery of power.

C-rates
C-rates specify charge and discharge currents. At 1C, the battery charges and discharges at a current that is par with the marked Ah rating; at 0.5C the current is half, and at 0.1C it is one tenth. On charge, 1C charges a good battery in about one hour; 0.5C takes 2 hours and 0.1C 10 to 14 hours. Read more about What is the C-rate?

Load
Also known as electromotive force (EMF), the load draws energy from the battery. Internal battery resistance and depleting state-of-charge cause the voltage to drop.

Watts and Volt-amps (VA)

Power drawn from a battery is expressed in watts (W) or volt-amps (VA). Watt is the real power that is being metered; VA is the apparent power that determines the wiring sizing and the circuit breakers. On a purely resistive load, watt and VA readings are alike; a reactive load such as an inductive motor or florescent light causes a drop in the power factor (pf) from the ideal one (1) to 0.7 or lower. For example, a pf of 0.7 has a power efficiency of 70.

Primary Batteries
The growth has been in secondary batteries (rechargeable) but non-rechargeable or primary batteries are equally important. They continue to fill an important niche market in applications such as wristwatches, remote controls, electric keys and childrens toys. Primary batteries also assist when charging is impractical or impossible, such as military combat, rescue missions and forest-fire services. Other applications of primary batteries are tire pressure gauges in cars and trucks, transmitters for bird tracking, pacemakers for heart patients, intelligent drill bits for mining,as well as light beacons and remote repeater stations. High specific energy, long storage times and operational

readiness make this battery well suited for such applications. The battery can be carried to remote locations and used instantly, even after long storage. Most primary batteries are inexpensive, readily available and environmentally friendly. Carbon-zinc, also known as the Leclanch battery, is the least expensive battery and comes with consumer devices when batteries are included. These general purpose batteries are used for applications with low power drain, such as remote controls, flashlights, childrens toys and wall clocks. One of the most common primary batteries for consumers is the alkaline-manganese, or alkaline for short. Lewis Urry invented it in 1949 while working with the Eveready Battery Company Laboratory in Parma, Ohio. Alkaline delivers more energy at higher load currents than carbon-zinc. Best of all, alkaline does not leak when depleted, as carbon-zinc does. On the negative side, alkaline is more expensive than carbon-zinc. Primary batteries have one of the highest energy densities. Although secondary batteries have improved, a regular household alkaline provides 50 percent more energy than lithium-ion. The most energy-dense primary is the lithium battery made for film cameras and military combat. It holds more than three times the energy of lithium-ion and comes in various blends, such as lithium-metal, lithium manganese dioxide, lithium-sulfur dioxide, lithium-thionyl chloride, lithium oxygen and others. Figure 1 compares the typical gravimetric energy densities of lead acid, NiMH, Li-ion, alkaline and lithium primary batteries.

Figure 1: Specific energy comparison of secondary and primary batteries Secondary batteries are typically rated at 1C; alkaline uses much lower discharge currents. Courtesy of Cadex Specific energy indicates the energy a battery can hold. This, however, does not guarantee delivery. Primary batteries tend to have high internal resistance, which limits

the discharge to light loads such as remote controls, flashlights and portable entertainment devices. Digital cameras are borderline a power drill on alkaline would be unthinkable. Manufacturers of primary batteries only specify specific energy; the specific power (ability to deliver power) is not published. While most secondary batteries are rated at a discharge current of 1C, the capacity of primary batteries is measured by discharging them at a very low current of 25mA, or a fraction of a C. In addition, the batteries are allowed to go down to a very low voltage of 0.8 volts per cell. This evaluation method provides impressive readings on paper, but the results are poor under a more demanding load. To compare primary and secondary batteries side by side, we discharge both types with a current of 1C and plot the results as Actual beside the already plotted Rated, which the manufacturer provides (Figure 2). While the primary batteries do well on the rated capacity with load currents similar to a portable entertainment device, secondary batteries have lower capacities but are more resilient at a load of 1C.

Figure 2: Energy comparison under load. Rated refers to a mild discharge; Actual is a load at 1C. High internal resistance limits alkaline battery to light loads. Courtesy of Cadex The reason for the sharp performance drop on primary batteries is the high internal resistance, which causes the voltage to drop under load. The already high resistance increases further as the battery depletes on discharge. When the battery goes flat on a digital camera, for example, precious capacity is often left behind. A spent alkaline can often power a kitchen clock for two years. Figure 1-10 shows the largest discrepancy between Rated and Actual on alkaline. A long-life alkaline (not shown on chart) will deliver better results.

Table 3 illustrates the capacity of standard alkaline batteries with loads that are typical of personal entertainment devices or small flashlights. Discharging at fractional C-rates produces high capacities; increasing the discharge rate would drastically reduce it.

Table 3: Alkaline specifications. The discharge resembles entertainment devices with low loads. Courtesy of Panasonic The use of primary batteries can be expensive, and the inability to recharge increases the cost of power by about thirty fold over secondary batteries. The pricing issue becomes even more acute if the packs are being replaced after each mission, regardless of length of service. Discarding partially used batteries is common, especially in fleet applications and critical missions. It is more convenient and safer to simply issue the troops fresh packs with each call rather than estimating the remaining state-of-charge. A US Army general once said that half of the batteries discarded still have 50 percent energy left. Estimating the battery state-of-charge would help, but such instruments are expensive and inaccurate. The most basic method is measuring the open circuit voltage and reading the internal resistance by applying a brief load and checking the voltage drop. A large voltage differential would relate to rising resistance, a hint to the end of life. A more accurate way is to count the out-flowing energy, a measurement that is also known as coulomb counting, but this requires expensive circuitry. See How to Measure State-of-charge. Due to high cost and inherent inaccuracies, fuel gauges are seldom used on primary batteries.

Secondary Batteries
Rechargeable batteries play an important role in our life and many daily chores would be unthinkable without the ability to recharge an empty battery. Points of interest are specific energy, years of service life, load characteristics, safety, price, self-discharge, environmental issues, maintenance requirements, and disposal. Lead Acid One of the oldest rechargeable battery systems; is rugged, forgiving if abused and economical in price; has a low specific energy and limited cycle life. Lead acid is used for wheelchairs, golf cars, personnel carriers, emergency lighting and uninterruptible power supply (UPS).

Nickel-cadmium (NiCd) Mature and well understood; is used where long service life, high discharge current, extreme temperatures and economical price are of importance. Due to environmental concerns, NiCd is being replaced with other chemistries. Main applications are power tools, two-way radios, aircraft and UPS. Nickel-metal-hydride (NiMH) A practical replacement for NiCd; has higher specific energy with fewer toxic metals. NiMH is used for medical instruments, hybrid cars and industrial applications. NiMH is available in AA and AAA cells for consumer use. Lithium-ion (Li-ion) Most promising battery systems; is used for portable consumer products as well as electric powertrains for vehicles; is more expensive than nickel- and lead acid systems and needs protection circuit for safety. The lithium-ion family is divided into three major battery types, so named by their cathode oxides, which are cobalt, manganese and phosphate. The characteristics of these Li-ion systems are as follows. Lithium-ion-cobalt or lithium-cobalt (LiCoO2): Has high specific energy with moderate load capabilities and modest service life. Applications include cell phones, laptops, digital cameras and wearable products. Lithium-ion-manganese or lithium-manganese (LiMn2O4): Is capable of high charge and discharge currents but has low specific energy and modest service life; used for power tools, medical instruments and electric powertrains. Lithium-ion-phosphate or lithium-phosphate (LiFePO4): Is similar to lithiummanganese; nominal voltage is 3.3V/cell; offers long cycle life, has a good safe record but exhibits higher self-discharge than other Li-ion systems. There are many other lithium-ion based batteries, some of which are described further on this website. Missing in the list is also the popular lithium-ion-polymer, or Lipolymer. While Li-ion systems get their name from their unique cathode materials, Lipolymer differs by having a distinct architecture. Nor is the rechargeable lithium-metal mentioned. This battery requires further development to control dendrite growth, which can compromise safety. Once solved, Li-metal will become an alternative battery choice with extraordinary high specific energy and good specific power. Table 1 compares the characteristics of four commonly used rechargeable battery systems showing average performance ratings at time of publication.

Table 1: Characteristics of commonly used rechargeable batteries The figures are based on average ratings of commercial batteries at time of publication; experimental batteries with above-average ratings are excluded. Internal resistance of a battery pack varies with milliampere-hour (mAh) rating, wiring and number of cells. Protection circuit of lithium-ion adds about 100mW. 2 Based on 18650 cell size. Cell size and design determines internal resistance. 3 Cycle life is based on battery receiving regular maintenance. 4 Cycle life is based on the depth of discharge (DoD). Shallow DoD improves cycle life. 5 Self-discharge is highest immediately after charge. NiCd loses 10% in the first 24 hours, then declines to 10% every 30 days. High temperature increases self-discharge. 6 Internal protection circuits typically consume 3% of the stored energy per month. 7 The traditional voltage is 1.25V; 1.2V is more commonly used. 8 Low internal resistance reduces the voltage drop under load and Li-ion is often
1

rated higher than 3.6V/cell. Cells marked 3.7V and 3.8V are fully compatible with 3.6V. 9 Capable of high current pulses; needs time to recuperate. 10 Applies to discharge only; charge temperature is more confined. 11 Maintenance may be in the form of equalizing or topping charge to prevent sulfation.

Battery Types

Lead-based Batteries
Invented by the French physician Gaston Plant in 1859, lead acid was the first rechargeable battery for commercial use. Despite its advanced age, the lead chemistry continues to be in wide use today, and there are good reasons for its popularity; lead acid is dependable and inexpensiveon cost-per-watt base. There are few other batteries that deliver bulk power as cheaply as lead acid, and this makes the battery cost-effective for automobiles, golf cars, forklifts, marine and uninterruptible power supplies (UPS). But lead acid has disadvantages; it is heavy and is less durable than nickel- and lithiumbased systems when deep-cycled. A full discharge causes strain and each discharge/charge cycle permanently robs the battery of a small amount of capacity. This loss is small while the battery is in good operating condition, but the fading increases once the performance drops to half the nominal capacity. This wear-down characteristic applies to all batteries in various degrees. Depending on the depth of discharge, lead acid for deep-cycle applications provides 200 to 300 discharge/charge cycles. The primary reasons for its relatively short cycle life are grid corrosion on the positive electrode, depletion of the active material and expansion of the positive plates. These changes are most prevalent at elevated operating temperatures and high-current discharges. See How to Prolong Lead Acid Batteries. Charging a lead acid battery is simple but the correct voltage limits must be observed, and here there are compromises. Choosing alow voltage limit shelters the battery but this produces poor performance and causes a buildup of sulfation on the negative plate. A high voltage limit improves performance but form grid corrosion on the positive plate. While sulfation can be reversed if serviced in time, corrosion is permanent. See Charging Lead Acid. Lead acid does not lend itself to fast charging and with most types, a full charge takes 14 to16 hours. The battery must always be stored at full state-of-charge. Low charge causes sulfation, a condition that robs the battery of performance. Adding carbon on the negative electrode reduces this problem but this lowers the specific energy. See New Lead Acid Systems. Lead acid has a moderate life span and is not subject to memory as nickel-based systems are. Charge retention is best among rechargeable batteries. While NiCd loses approximately 40 percent of its stored energy in three months, lead acid self-discharges

the same amount in one year. Lead acid work well at cold temperatures and is superior to lithium-ion when operating in subzero conditions.

Sealed Lead Acid

The first sealed, or maintenance-free, lead acid emerge in the mid-1970s. The engineers argued that the term sealed lead acid is a misnomer because no lead acid battery can be totally sealed. This is true and battery designers added a valve to control venting of gases during stressful charge and rapid discharge. Rather than submerging the plates in a liquid, the electrolyte is impregnated into a moistened separator, a design that resembles nickel- and lithium-bases system. This enables to operate the battery in any physical orientation without leakage. The sealed battery contains less electrolyte than the flooded type, hence the term acidstarved. Perhaps the most significant advantage of the sealed lead acid is the ability to combine oxygen and hydrogen to create water and prevent water loss. The recombination occurs at a moderate pressure of 0.14 bar (2psi). The valve serves as safety vent if gases buildup during over-overcharge or stressful discharge. Repeated venting would lead to an eventual dry out. Driven by these advantages, several types of sealed lead acid have emerged and the most common are gel, also known as valve-regulated lead acid (VRLA), and absorbent glass mat (AGM). The gel cell contains a silica type gel that suspends the electrolyte in a paste. Smaller packs with capacities of up to 30A are called SLA (sealed lead acid). Packaged in a plastic container, these batteries are used for small UPS, emergency lighting, ventilators for healthcare and wheelchairs. Because of economical price, dependable service and low maintenance, the SLA remains the preferred choice for biomedical and healthcare in hospitals and retirement homes. The VRLA is the larger gel variant used as power backup for cellular repeater towers, Internet hubs, banks, hospitals, airports and other sites. The AGM is a newer design and suspends the electrolytein aspecially designed glass mat. This offers several advantages to lead acid systems, including faster charging and instant high load currents on demand. AGM works best as a mid-range battery with capacities of 30 to 100Ah and is less suited for large systems, such as UPS. Typical uses are starter batter for motorcycles, start-stop function for micro-hybrid cars, as well as marine and RV that need some cycling. With cycling and age, the capacity of AGM fades gradually; gel, on the other hand, has a dome shaped performance curve and stays in the high performance range longer but then drops suddenly towards the end of life. AGM is more expensive than flooded, but is cheaper than gel.(Gel would be too expensive for start/stop use in cars.) See Absorbent Glass Mat (AGM). Unlike the flooded, the sealed lead acid battery is designed with a low over-voltage potential to prohibit the battery from reaching its gas-generating potential during charge. Excess charging causes gassing, venting and subsequent water depletion and dry out. Consequently, gel, and in part also AGM, cannot be charged to their full potential and the charge voltage limit must be set lower than that of a flooded. The float charge on full charge must also be lowered. In respect to charging, the gel and AGM are no direct

replacements to the flooded type. If no designated charger is available with lower voltage settings, disconnect the charger after 24 hours of charge. This prevents gassing due to a float voltage that is set too high. See Charging Lead Acid. The optimum operating temperature for a VRLA battery is 25C (77F); every 8C (15F) rise above this temperature threshold cuts battery life in half. See Heat, Loading and Battery Life. Lead acid batteries are rated at a 5-hour (0.2C) and 20-hour (0.05C) discharge. The battery performs best when discharged slowly and the capacity readings are notably higher at a slow discharge rate. Lead acid can, however, deliver high pulse currents of several C if done for only a few seconds. This makes the lead acid well suited as a starter battery, also known as starter-light-ignition (SLI). The high lead content and the sulfuric acid make lead acid environmentally unfriendly. The following paragraphs look at the different architectures within the lead acid family and explain why one battery type does not fit all.

Starter and Deep-cycle Batteries

The starter battery is designed to crank an engine with a momentary high power burst; the deep-cycle battery, on the other hand, is built to provide continuous power for a wheelchair or golf car. From the outside, both batteries look alike; however, there are fundamental differences in design. While the starter battery is made for high peak power and does not like deep cycling, the deep-cycle battery has a moderate power output but permits cycling. Lets examine the architectural difference between these batteries further. Starter batteries have a CCA rating imprinted in amperes; CCA refers to cold cranking amps, which represents the amount of current a battery can deliver at cold temperature. SAE J537 specifies 30 seconds of discharge at 18C (0F) at the rated CCA ampere without dropping below 7.2 volts. (SAE stands for Society of Automotive Engineers.) Starter batteries have a very low internal resistance, and the manufacturer achieves this by adding extra plates for maximum surface area (Figure 1). The plates are thin and the lead is applied in a sponge-like form that has the appearance of fine foam. This method extends the surface area of the plates to achieve low resistance and maximum power. Plate thickness isless important here because the discharge is short and the battery is recharged while driving;the emphasis is on power rather than capacity. Figure 1: Starter battery The starter battery has many thin plates in parallel to achieve low resistance with high surface area. The starter battery does not allow deep cycling. Courtesy of Cadex Deep-cycle lead acid batteries for golf cars, scooters and wheelchairs are built for maximum capacity and high cycle count. The manufacturer achieves this by making the

lead plates thick (Figure 2). Although the battery is designed for cycling, full discharges still induce stress, and the cycle count depends on the depth-of-discharge (DoD). Deepcycle batteries are marked in Ah or minute of runtime. Figure 2: Deep-cycle battery The deep-cycle battery has thick plates for improved cycling abilities. The deep-cycle battery generally allows about 300 cycles. Courtesy of Cadex A starter battery cannot be swapped with a deep-cycle battery and vice versa. While an inventive senior may be tempted to install a starter battery instead of the more expensive deep-cycle on his wheelchair to save money, the starter battery wont last because the thin sponge-like plates would quickly dissolve with repeated deep cycling. There are combination starter/deep-cycle batteries available for trucks, buses, public safety and military vehicles, but these units are big and heavy. As a simple guideline, the heavier the battery is, the more lead it contains, and the longer it will last. Table 3 compares the typical life of starter and deep-cycle batteries when deep-cycled. Depth of Discharge 100% 50% 30% Starter Battery 1215 cycles 100120 cycles 130150 cycles Deep-cycle Battery 150200 cycles 400500 cycles 1,000 and more cycles

Table 3: Cycle performance of starter and deep-cycle batteries. A discharge of 100% refers to a full discharge; 50% is half and 30% is a moderate discharge with 70% remaining. Lead is toxic and environmentalists would like to replace the lead acid battery with another chemistry. Europe succeeded to keep nickel-cadmium batteries out of consumer products, and authorities try to do it with the starter battery. The choices are NiMH and lithium-ion, but at a price tag of $3,000 for Li-ion, this will not fly. In addition, Li-ion has poor performance at sub-freezing temperature. Regulators hope that advancements in the electric powertrain will lower the cost, but such a large price reduction to match the low-cost lead acid may not be possible. Lead acid will continue to be the battery of choice to crank the engines. Table 4 spells out the advantages and limitations of common lead acid batteries in use today. Inexpensive and simple to manufacture; low cost per watt-hour Advantages Low self-discharge; lowest among rechargeable batteries

High specific power, capable of high discharge currents Good low and high temperature performance Low specific energy; poor weight-to-energy ratio Slow charge; fully saturated charge takes 14 hours Must be stored in charged condition to prevent sulfation Limitations Limited cycle life; repeated deep-cycling reduces battery life Flooded version requires watering Transportation restrictions on the flooded type Not environmentally friendly

Table 4: Advantages and limitations of lead acid batteries. Dry systems have advantages over flooded but are less rugged.

Absorbent Glass Mat (AGM)

AGM technology was developed in 1985 for military aircraft to reduce weight, increase power handling and improve reliability. The acid is absorbed by a very fine fiberglass mat, making the battery spill-proof. This enables shipment without hazardous material restrictions. The plates can be made flat to resemble a standard flooded lead acid pack in a rectangular case; they can also be wound into a cylindrical cell. AGM has very low internal resistance, is capable to deliver high currents on demand and offers a relatively long service life, even when deep-cycled. AGM is maintenance free, provides good electrical reliability and is lighter than the flooded lead acid type. It stands up well to low temperatures and has a low self-discharge. The leading advantages are a charge that is up to five times faster than the flooded version, and the ability to deep cycle. AGM offers a depth-of-discharge of 80 percent; the flooded, on the other hand, is specified at 50 percent DoD to attain the same cycle life. The negatives are slightly lower specific energy and higher manufacturing costs that the flooded. AGM has a sweet spot in midsize packs from 30 to 100Ah and is less suitable for large UPS system. AGM batteries are commonly built to size and are found in high-end vehicles to run power-hungry accessories such as heated seats, steering wheels, mirrors and windshields. NASCAR and other auto racing leagues choose AGM products because they are vibration resistant. AGM is the preferred battery for upscale motorcycles. Being sealed, AGM reduces acid spilling in an accident, lowers the weight for the same performance and allows installation at odd angles. Because of good performance at cold temperatures, AGM batteries are also used for marine, motor home and robotic applications.

Ever since Cadillac introduced the electric starter motor in 1912, lead acid became the natural choice to crank the engine. The classic flooded type is, however, not robust enough for the start-stop function and most batteries in a micro-hybrid car are AGM. Repeated cycling of a regular flooded type causes a sharp capacity fade after two years of use. See Heat, Loading and Battery Life. As with all gelled and sealed units, AGM batteries are sensitive to overcharging. These batteries can be charged to 2.40V/cell (and higher) without problem; however, the float charge should be reduced to between 2.25 and 2.30V/cell (summer temperatures may require lower voltages). Automotive charging systems for flooded lead acid often have a fixed float voltage setting of 14.40V (2.40V/cell), and a direct replacement with a sealed unit could spell trouble by exposing the battery to undue overcharge on a long drive. See Charging Lead Acid. AGM and other sealed batteries do not like heat and should be installed away from the engine compartment. Manufacturers recommend halting charge if the battery core reaches 49C (120F). While regular lead acid batteries need a topping charge every six months to prevent the buildup of sulfation, AGM batteries are less prone to this and can sit in storage for longer before a charge becomes necessary. Table 1 spells out the advantages and limitations of AGM.

Spill-proof through acid encapsulation in matting technology High specific power, low internal resistance, responsive to load Up to 5 times faster charge than with flooded technology Advantages Better cycle life than with flooded systems Water retention (oxygen and hydrogen combine to produce water) Vibration resistance due to sandwich construction Stands up well to cold temperature Higher manufacturing cost than flooded (but cheaper than gel) Sensitive to overcharging (gel has tighter tolerances than AGM) Capacity has gradual decline (gel has a performance dome) Limitations Low specific energy Must be stored in charged condition (less critical than flooded) Not environmentally friendly (has less electrolyte, lead that flooded) Table 4: Advantages and limitations AGM. The gel system shares many of the characteristics.

New Lead Acid Systems

Lead acid batteries continue to hold a leading position, especially in wheeled mobility and stationary applications. This strong market appeal entices manufacturers to explore ways to make the batteries better. Improvements have been made and some claims are so promising that one questions the trustworthiness. It is no secret that researchers prefer publishing the positive attributes while keeping the negatives under wraps. The following information on lead acid developments was obtained from available printed resources at the time of writing.

Firefly Energy
The composite plate material of the Firefly Energy battery is based on a lead acid variant that is lighter, longer living and has higher active material utilization than current lead acid systems. The battery includes foam electrodes for the negative plates, which gives it a performance that is comparable to NiMH but at lower manufacturing costs. Design concerns include microtubule blockage through crystal growth during low charge conditions. In addition, crystal expansion causes a reduction of the surface area, which will result in lower capacity with aging. Pricing is also a concern. It currently costs about $450 to manufacture a Firefly battery as opposed to $150 for a regular lead acid version. Firefly Energy is a spin-off of Caterpillar and went into bankruptcy in 2010.

Altraverda Bipolar
Similar to the Firefly Energy battery, the Altraverda battery is based on lead. It uses a proprietary titanium sub-oxide ceramic structure, called Ebonex, for the grid and an AGM separator. The un-pasted plate contains Ebonex particles in a polymer matrix that holds a thin lead alloy foil on the external surfaces. With 5060Wh/kg, the specific energy is about one-third larger than regular lead acid and is comparable with NiCd. Based in the UK, Altraverda works with East Penn in the USA, and the battery is well suited for higher voltage applications.

Axion Power
The Axion Power e3 Supercell is a hybrid battery/ultracapacitor in which the positive electrode consists of standard lead dioxide and the negative electrode is activated carbon, while maintaining an assembly process that is similar to lead acid. The Axion Power battery offers faster recharge times and longer cycle life on repeated deep discharges than what is possible with regular lead acid systems. This opens the door for the start-stop application in micro-hybrid cars. The lead-carbon combination of the Axion Power battery lowers the lead content on the negative plate, which results in a weight reduction of 30 percent compared to a regular lead acid. This, however, also lowers the specific energy to 1525Wh/kg instead of 3050Wh/kg, which a regular lead acid battery normally provides.

CSIRO Ultrabattery
The CSIRO Ultrabattery combines an asymmetric ultracapacitor and a lead acid battery in each cell. The capacitor enhances the power and lifetime of the battery by acting as a buffer during charging and discharging, prolonging the lifetime by a factor of four over customary lead acid systems and producing 50 percent more power. The manufacturer also claims that the battery is 70 percent cheaper to produce than current hybrid electric vehicle (HEV) batteries. CSIRO batteries are undergoing road trials in a Honda Insight HEV and show good results. Furukawa Battery in Japan licensed the technology. The CSIRO battery is also being tested for start-stop applications in micro-hybrid cars to replace the lead acid starter battery. This battery promises extended life when exposed to frequent start-stop conditions and is able to take a fast charge.

EEStor
This is the mystery battery/ultracapacitor combination that receives much media attention. The battery is based on a modified barium titanate ceramic powder and claims a specific energy of up to 280Wh/kg, higher than lithium-ion. The company is very secretive about their invention and releases only limited information. Some of their astonishing claims are: One-tenth of the weight of a NiMH battery in a hybrid application, no deep-cycle wear-down, three- to six-minute charge time, no hazardous material, similar manufacturing costs to lead acid, and a self-discharge that is only 0.02 percent per month, a fraction of that of lead acid and Li-ion.

Nickel-based Batteries
The following section describes nickel-based batteries, and we begin with nickel-cadmium (NiCd), an older chemistry for which extensive data is available. Much of these characteristics also apply to nickel-metal-hydride (NiMH), as these two systems are close cousins. The toxicity of NiCd is limiting this solid and robust battery to specialty applications.

Nickel-cadmium (NiCd)
The nickel-cadmium battery, invented by Waldmar Jungner in 1899, offered several advantages over lead acid, but the materials were expensive and the early use was restricted. Developments lagged until 1932 when attempts were made to deposit the active materials inside a porous nickel-plated electrode. Further improvements occurred in 1947 by trying to absorb the gases generated during charge. This led to the modern sealed NiCd battery in use today. For many years, NiCd was the preferred battery choice for two-way radios, emergency medical equipment, professional video cameras and power tools. In the late 1980s, the ultra-highcapacity NiCd rocked the world with capacities that were up to 60 percent higher than the standard NiCd. This was done by packing more active material into the cell, but the gain was met with the side effects of higher internal resistance and shorter cycle. The standard NiCd remains one of the most rugged and forgiving batteries but needs proper care to attain longevity. It is perhaps for this reason that NiCd is the favorite battery of many engineers. Table 1 lists the advantages and limitations of the standard NiCd.

Fast and simple charging even after prolonged storage High number of charge/discharge cycles; provides over 1,000 charge/discharge cycles with proper maintenance Good load performance; rugged and forgiving if abused Advantages Long shelf life; can be stored in a discharged state Simple storage and transportation; not subject to regulatory control Good low-temperature performance Economically priced; NiCd is the lowest in terms of cost per cycle Available in a wide range of sizes and performance options Relatively low specific energy compared with newer systems Memory effect; needs periodic full discharges Limitations Environmentally unfriendly; cadmium is a toxic metal and cannot be disposed of in landfills High self-discharge; needs recharging after storage Table 1: Advantages and limitations of NiCd batteries

Nickel-metal-hydride (NiMH)
Research of nickel-metal-hydride started in 1967; however, instabilities with the metal-hydride led scientists to develop the nickel-hydrogen battery (NiH) instead. Today, NiH is mainly used in satellites. New hydride alloys discovered in the 1980s offered better stability and the development of NiMH advanced in earnest. Today, NiMH provides 40 percent higher specific energy than a standard NiCd, but the decisive advantage is the absence of toxic metals. The advancements of NiMH are impressive. Since 1991, the specific energy has doubled and the life span extended. The hype of lithium-ion may have dampened the enthusiasm for NiMH a bit but not to the point to turn HEV makers away from this proven technology. Batteries for the electric powertrain in vehicles must meet some of the most demanding challenges, and NiMH has two major advantages over Li-ion here. These are price and safety. Makers of hybrid vehicles claim that NiMH costs one-third of an equivalent Li-ion system, and the relaxation on safety provisions contribute in part to this price reduction. Nickel-metal-hydride is not without drawbacks. For one, it has a lower specific energy than Liion, and this is especially true with NiMH for the electric powertrain. The reader should be reminded that NiMH and Li-ion with high energy densities are reserved for consumer products; they would not be robust enough for the hybrid and electric vehicles. NiMH and Li-ion for the electric powertrain have roughly one-third less capacity than consumer batteries. NiMH also has high self-discharge and loses about 20 percent of its capacity within the first 24 hours, and 10 percent per month thereafter. Modifying the hydride materials lowers the selfdischarge and reduces corrosion of the alloy, but this decreases the specific energy. Batteries

for the electric powertrain make use of this modification to achieve the needed robustness and life span. There are strong opinions and preferences between battery chemistries, and some experts say that NiMH will serve as an interim solution to the more promising lithium systems. There are many hurdles surrounding Li-ion also and these are cost and safety. Li-ion cells are not offered to the public in AA, AAA and other popular sizes in part because of safety. Even if they were made available, Li-ion has a higher voltage compared to nickel-based batteries.

Consumer Application
NiMH has become one of the most readily available and low-cost rechargeable batteries for portable devices. NiMH is non-toxic and offers a higher specific energy than NiCd. Battery manufacturers, such as Sanyo, Energizer, Duracell and GP, have recognized the need for a durable and low-cost rechargeable battery for consumers and offer NiMH in AA and AAA sizes. The battery manufacturers hope to persuade buyers to switch to rechargeable batteries and reduce the environmental impact of throwaway primary cells. The NiMH battery for the consumer market can be viewed as an alternative to the failed reusable alkaline that appeared in the 1990s. Limited cycle life and poor loading characteristics hindered its success. What is of ongoing concern to the consumer using rechargeable batteries is the high selfdischarge, and NiMH behaves like a leaky basketball or bicycle tire. A flashlight or portable entertainment device with a NiMH battery gets flat when put away for only a few weeks. Having to recharge the device before each use does not sit well. The Eneloop NiMH by Sanyo has reduced the self-discharge by a factor of six. This means that you can store the charged battery six times longer than a regular NiMH before a recharge becomes necessary. The drawback is a slightly lower specific energy compared to a regular NiMH. Other NiMH manufacturers such as ReCyko by GP claim similar results. Table 2 summarizes the advantages and limitations of industrial-grade NiMH. The table does not include the Eneloop and equivalent consumer brands.

3040 percent higher capacity than a standard NiCd Less prone to memory than NiCd Advantages Simple storage and transportation; not subject to regulatory control Environmentally friendly; contains only mild toxins Nickel content makes recycling profitable Limited service life; deep discharge reduces service life Requires complex charge algorithm Limitations Does not absorb overcharge well; trickle charge must be kept low Generates heat during fast-charge and high-load discharge High self-discharge; chemical additives reduce self-discharge at the

expense of capacity Performance degrades if stored at elevated temperatures; should be stored in a cool place at about 40 percent state-of-charge Table 2: Advantages and limitations of NiMH batteries

Lithium-based Batteries
Pioneer work with the lithium battery began in 1912 under G.N. Lewis, but it was not until the early 1970s that the first non-rechargeable lithium batteries became commercially available. Attempts to develop rechargeable lithium batteries followed in the 1980s but the endeavor failed because of instabilities in the metallic lithium used as anode material. Lithium is the lightest of all metals, has the greatest electrochemical potential and provides the largest specific energy per weight. Rechargeable batteries with lithium metal on the anode (negative electrodes)* could provide extraordinarily high energy densities; however, it was discovered in the mid 1980s that cycling produced unwanted dendrites on the anode. These growth particles penetrate the separator and cause an electrical short. When this occurs, the cell temperature rises quickly and approaches the melting point of lithium, causing thermal runaway, also known as venting with flame. A large number of rechargeable metallic lithium batteries sent to Japan were recalled in 1991 after a battery in a mobile phone released flaming gases and inflicted burns to a mans face. The inherent instability of lithium metal, especially during charging, shifted research to a non-metallic solution using lithium ions. Although lower in specific energy than lithium-metal, Li-ion is safe, provided cell manufacturers and battery packers follow safety measures in keeping voltage and currents to secure levels. Read more about Protection Circuits. In 1991, Sony commercialized the first Li-ion battery, and today this chemistry has become the most promising and fastest growing on the market. Meanwhile, research continues to develop a safe metallic lithium battery. The specific energy of Li-ion is twice that of NiCd, and the high nominal cell voltage of 3.60V as compared to 1.20V for nickel systems contributes to this gain. Improvements in the active materials of the electrode have the potential of further increases in energy density. The load characteristics are good, and the flat discharge curve offers effective utilization of the stored energy in a desirable voltage spectrum of 3.70 to 2.80V/cell. Nickel-based batteries also have a flat discharge curve that ranges from 1.25 to 1.0V/cell. In 1994, the cost to manufacture Li-ion in the 18650** cylindrical cell with a capacity of 1,100mAh was more than $10. In 2001, the price dropped to $2 and the capacity rose to 1,900mAh. Today, high energy-dense 18650 cells deliver over 3,000mAh and the costs have dropped further. Cost reduction, increase in specific energy and the absence of toxic material paved the road to make Li-ion the universally accepted battery for portable application, first in the consumer industry and now increasingly also in heavy industry, including electric powertrains for vehicles.

In 2009, roughly 38 percent of all batteries by revenue were Li-ion. Li-ion is a lowmaintenance battery, an advantage many other chemistries cannot claim. The battery has no memory and does not need exercising (deliberate full discharge) to keep in shape. Self-discharge is less than half that of nickel-based systems. This makes Li-ion well suited for fuel gauge applications. The nominal cell voltage of 3.60V can directly power cell phones and digital cameras, offering simplifications and cost reductions over multi-cell designs. The drawbacks are the need for protection circuits to prevent abuse, as well as high price.

Types of Lithium-ion Batteries

Similar to the lead- and nickel-based architecture, lithium-ion uses a cathode (positive electrode), an anode (negative electrode) and electrolyte as conductor. The cathode is a metal oxide and the anode consists of porous carbon. During discharge, the ions flow from the anode to the cathode through the electrolyte and separator; charge reverses the direction and the ions flow from the cathode to the anode. Figure 1 illustrates the process. Figure 1: Ion flow in lithium-ion battery. When the cell charges and discharges, ions shuttle between cathode (positive electrode) and anode (negative electrode). On discharge, the anode undergoes oxidation, or loss of electrons, and the cathode sees a reduction, or a gain of electrons. Charge reverses the movement. Li-ion batteries come in many varieties but all have one thing in common the catchword lithium-ion. Although strikingly similar at first glance, these batteries vary in performance, and the choice of cathode materials gives them their unique personality. Common cathode materials are Lithium Cobalt Oxide (or Lithium Cobaltate), Lithium Manganese Oxide (also known as spinel or Lithium Manganate), Lithium Iron Phosphate, as well as Lithium Nickel Manganese Cobalt (or NMC)*** and Lithium Nickel Cobalt Aluminum Oxide (or NCA). All these materials possess a theoretical specific energy with given limits. (Lithium-ion has a theoretically capacity of about 2,000kWh. This is more than 10 times the specific energy of a commercial Li-ion battery.)

Sonys original lithium-ion battery used coke as the anode (coal product). Since 1997, most Li-ion manufacturers, including Sony, have shifted to graphite to attain a flatter discharge curve. Graphite is a form of carbon that is also used in the lead pencil. It stores lithium-ion well when the battery is charged and has long-term cycle stability. Among the carbon materials, graphite is the most commonly used, followed by hard and soft carbons. Other carbons, such as carbon nanotubes, have not yet found commercial use. Figure 2-8 illustrates the voltage discharge curve of a modern Li-ion with graphite anode and the early coke version.

Figure 2: Voltage discharge curve of lithium-ion A battery should have a flat voltage curve in the usable discharge range. The modern graphite anode does this better than the early coke version. Courtesy of Cadex

Developments also occur on the anode and several additives are being tried, including silicon-based alloys. Silicon achieves a 20 to 30 percent increase in specific energy at the cost of lower load currents and reduced cycle life. Nano-structured lithium-titanate as an anode additive shows promising cycle life, good load capabilities, excellent lowtemperature performance and superior safety, but the specific energy is low. Mixing cathode and anode material allows manufacturers to strengthen intrinsic qualities; however, enhancing one attribute may compromise another. Battery makers can, for example, optimize the specific energy (capacity) to achieve extended runtime, increase the specific power for improved current loading, extend service life for better longevity, and enhance safety to endure environmental stresses. But there are drawbacks. A higher capacity reduces the current loading; optimizing current loading lowers the specific energy; and ruggedizing a cell for long life and improved safety increases battery size and adds to cost due to a thicker separator. The separator is said to be the most expensive part of a battery. Manufacturers can attain a high specific energy and low cost relatively easily by adding nickel in lieu of cobalt, but this makes the cell less stable. While a start-up company may focus on high specific energy to gain quick market acceptance, safety and durability cannot be compromised. Reputable manufacturers place high integrity on safety and longevity.

Table 3 summarizes the characteristics of Li-ion with different cathode material. The table limits the chemistries to the four most commonly used lithium-ion systems and applies the short form to describe them. The batteries are Li-cobalt, Li-manganese, Liphosphate and NMC. NMC stands for nickel-manganese-cobalt, a chemistry that is relatively new and can be tailored for applications needing either high capacity or high loading capabilities. Lithium-ion-polymer is not mentioned as this is not a unique chemistry and only differs in construction. Li-polymer can be made in various chemistries and the most widely used format is Li-cobalt.

Specifications Voltage Charge limit Cycle life2 Operating temperature

Li-cobalt LiCoO2 (LCO) 3.60V 4.20V 5001,000 Average

Li-manganese Li-phosphate LiMn2O4 (LMO) LiFePO4 (LFP) 3.80V 4.20V 5001,000 Average 3.30V 3.60V 1,0002,000 Good 90120Wh/kg

NMC1 LiNiMnCoO2 3.60/3.70V 4.20V 1,0002,000 Good 140-180Wh/kg

Specific energy 150190Wh/kg 100135Wh/kg Specific power 1C 10C, 40C pulse

35C continuous 10C Very safe, needs cell balancing and V protection. 270C (518F) High 1999 Safer than Licobalt. Needs cell balancing and protection. 210C (410F) High 2003

Safety

Average. Requires protection circuit and cell balancing of multi cell pack. Requirements for small formats with 1 or 2 cells can be relaxed 150C (302F) Raw material high 1994 250C (482F) Moli Energy, NEC Hitachi, Samsung 1996 Hitachi, Samsung, Sanyo, GS Yuasa, LG Chem, Toshiba Moli Energy, NEC High power, good to high specific energy; power tools, medical, EVs

Thermal. runaway3 Cost In use since

Sony, Sanyo, GS Yuasa, LG Researchers, Chem Samsung manufacturers Hitachi, Toshiba Very high specific energy, limited power; cell phones, laptops

A123, Valence, Sony, Sanyo, LG GS Yuasa, Chem, GS Yuasa, BYD, JCI/Saft, Hitachi Samsung Lishen High power, average specific energy, elevated selfdischarge Very high specific energy, high power; tools, medical, EVs

Notes

Table 3: Characteristics of the four most commonly used lithium-ion batteries Specific energy refers to capacity (energy storage); specific power denotes load capability. NMC, NCM, CMN, CNM, MNC and MCN are basically the same. The stoichiometry is usually Li[Ni(1/3)Co(1/3)Mn(1/3)]O2. The order of Ni, Mn and Co does not matter much. Application and environment govern cycle life; the numbers do not always apply correctly.
3 2 1

A fully charged battery raises the thermal runaway temperature, a partial charge lowers it.

Never was the competition to find an ideal battery more intense than today. Manufacturers see new applications for automotive propulsion systems, as well as stationary and grid storage, also knows as load leveling. At time of writing, the battery industry speculates that the Li-manganese and/or NMC might be the winners for the electric powertrain. Industrys experience has mostly been in portable applications, and the long-term suitability of batteries for automotive use is still unknown. A clear assessment of the cycle life, performance and long-term operating cost will only be known after having gone through a few generations of batteries for vehicles with electric powertrains, and more is known about the customers behavior and climate conditions under which the batteries are exposed. Table 4 summarizes the advantages and limitations of Li-ion.

High energy density Advantages Relatively low self-discharge; less than half that of NiCd and NiMH Low maintenance. No periodic discharge is needed; no memory. Requires protection circuit to limit voltage and current Subject to aging, even if not in use (aging occurs with all batteries and modern Li-ion systems have a similar life span to other chemistries) Transportation regulations when shipping in larger quantities Table 4: Advantages and limitations of Li-ion batteries

Limitations

* When consuming power, as in a diode, vacuum tube or a battery on charge, the anode is positive; when withdrawing power, as in a battery on discharge, the anode becomes negative.

** Standard of a cylindrical Li-ion cell developed in the mid 1990s; measures 18mm in diameter and 65mm in length; commonly used for laptops. Read more about Battery Formats. *** Some Lithium Nickel Manganese Cobalt Oxide systems go by designation of NCM, CMN, CNM, MNC and MCN. The systems are basically the same.

Types of Lithium-ion
The casual battery user may think there is only one lithium-ion battery. As there are many species of apple trees, so do also lithium-ion batteries vary and the difference lies mainly in the cathode materials. Innovative materials are also appearing in the anode to modify or replace graphite. Scientists prefer to name batteries by their chemical name and the material used, and unless you are a chemist, these terms might get confusing. Table 1 offers clarity by listing these batteries by their full name, chemical definition, abbreviations and short form. (When appropriate, this essay will use the short form.) To complete the list of popular Li-ion batteries, the table also includes NCA and Li-titanate, two lesser-known members of the Li-ion family.

Chemical name Lithium Cobalt Oxide1 Also Lithium Cobalate or lithium-ioncobalt) Lithium Manganese Oxide1 Also Lithium Manganate or lithium-ionmanganese Lithium Iron Phosphate1 Lithium Nickel Manganese Cobalt Oxide1, also lithium-

Material

Abbreviation

Short form

Notes

LiCoO2 (60% Co)

LCO

Li-cobalt

High capacity; for cell phone laptop, camera

LiMn2O4

LMO

LiFePO4

LFP

Li-manganese, or spinel Most safe; lower capacity than Li-cobalt but high specific power and long life. Li-phosphate Power tools, e-bikes, EV, medical, hobbyist.

LiNiMnCoO2 (1020% Co)

NMC

NMC

manganesecobalt-oxide Lithium Nickel Cobalt Aluminum Oxide1 Lithium Titanate2 LiNiCoAlO2 9% Co) Gaining importance in electric powertrain and grid storage

NCA

NCA

Li4Ti5O12

LTO

Li-titanate

Table 1: Reference names for Li-ion batteries.We willuse the short form when appropriate.
1

Cathode material

Anode material

To learn more about the unique characters and limitations of the six most common lithium-ion batteries, we use spider charts and look at the overall performance. We begin with Li-cobalt, the most commonly used battery for high-end consumer products, and then move to Li-manganese and Li- phosphate, batteries deployed in power tools, and finally address the newer players such as NME, NCA and Li-titanate.

Lithium Cobalt Oxide(LiCoO2)

Its high specific energy make Li-cobalt the popular choice for cell phones, laptops and digital cameras. The battery consists of a cobalt oxide cathode and a graphite carbon anode. The cathode has a layered structure and during discharge lithium ions move from the anode to the cathode. The flow reverses on charge. The drawback of Li-cobalt is a relatively short life span and limited load capabilities (specific power). Figure 2 illustrates the structure.

Figure 2: Li-cobalt structure The cathode has a layered structure. Duringdischarge the lithium ions move from the anode to the cathode; on charge the flow is from anode to cathode. Courtesy of Cadex Li-cobalt cannot be charged and discharged at a current higher than its rating. This means that an 18650 cell with 2,400mAh can only be charged and discharged at 2,400mA. Forcing a fast charge or applying a load higher than 2,400mA causes overheating and undue stress. For optimal fast charge, the manufacturer recommends a C-rate of 0.8C or 1920mA. [BU-402, What is C-rate?] The mandatory battery protection circuit limits the charge and discharge rate to a safe level of about 1C.

Figure 3 summarizes the performance of Li-cobalt in terms of specific energy,or capacity; specific power,or the ability to deliver high current; safety; performanceat hot and cold temperatures; life spanreflecting cycle life and longevity; and cost.The hexagonal spider web provides a quick and easy performance analysis of the battery characteristics.

Figure 3: Snapshot of an average Licobalt battery Li-cobalt excels on high specific energy but offers only moderate performance specific power, safety and life span. Courtesy of Cadex

Lithium Manganese Oxide (LiMn2O4)

Lithium insertion in manganese spinels was first published in the Materials Research Bulletin in 1983. In 1996, Moli Energy commercialized a Li-ion cell with lithium manganese oxide as a cathode material. The architecture forms a three-dimensional spinel structure that improves ion flow on the electrode, which results in lower internal resistance and improves current handling. A further advantage of spinel is high thermal stability and enhanced safety, but the cycle and calendar life is limited. Low internal cell resistance is key to fast charging and high-current discharging. In an 18650 package, Li-manganese can be discharged at currents of 2030A with moderate heat buildup. It is also possible to apply one-second load pulses of up to 50A. A continuous high load at this current would cause heat buildup and the cell temperature cannot exceed 80C (176F). Li-manganese is used for power tools, medical instruments, as well as hybrid and electric vehicles. Figure 4 shows the crystalline formation of the cathode in a three-dimensional framework. This spinel structure, which is usually composed of diamond shapes connected into a lattice, appears after initial formation.

Figure 4: Li-manganese structure The cathode crystalline formation of lithium manganese oxide has a threedimensional framework structure that appears after initial formation. Spinel provides low resistance but has a more moderate specific energy than cobalt. Courtesy of Cadex Li-manganese has a capacity that is roughly one-third lower compared to Li-cobalt but the battery still offers about 50 percent more energy than nickel-based chemistries. Design flexibility allows engineers to maximize the battery for either optimal longevity (life span), maximum load current (specific power) or high capacity (specific energy). For example, the long-life version in the 18650 cell has a moderate capacity of 1,100mAh; the high-capacity version is 1,500mAh but has a reduced service life. Laptop manufacturers would likely choose the high-capacity version for maximum runtime; whereas the maker of cars with the electric powertrain would take the long-life version with high specific power and sacrifice on runtime. Figure 5 shows the spider web of a typical Li-manganese battery. In this chart, all characteristics are marginal; however, newer designs have improved in terms of specific power, safety and life span.

Figure 5: Snapshot of a typical Limanganese battery Although moderate in overall performance, newer designs of Limanganese offer improvements in specific power, safety and life span. Courtesy of BCG research

Lithium Iron Phosphate(LiFePO4)

In 1996, the University of Texas (and other contributors) discovered phosphate as cathode material for rechargeable lithium batteries. Li-phosphate offers good electrochemical performance with low resistance. This is made possible with nano-scale phosphate cathode material. The key benefits are enhanced safety, good thermal stability, tolerant to abuse, high current rating and long cycle life. Storing a fully charged battery has minimal impact on the life span. As trade-off, the lower voltage of 3.3V/cell reduces the specific energy to slightly less than Li-manganese. In addition, cold temperature reduces performance, and elevated storage temperature shortens the

service life (better than lead acid, NiCd or NiMH). Li-phosphate has a higher selfdischarge than other Li-ion batteries, which can cause balancing issues with aging. Figure 6 summarizes the attributes of Li-phosphate.

Figure 6: Snapshot of a typical Liphosphate battery Li-phosphate has excellent safety and long life span but moderate specific energy and elevated self-discharge. Courtesy of BCG research

Lithium Nickel Manganese Cobalt Oxide (LiNiMnCoO2)

Leading battery manufacturers focus on a cathode combination of nickel-manganesecobalt (NMC). Similar to Li-manganese, these systems can also be tailored to high specific energy or high specific power, but not both. For example, NMC in an 18650 cell for consumer use can be tweaked to 2,250mAh, but the specific power is moderate. NMC in the same cell optimized for high specific power has a capacity of only 1,500mAh. A silicon-based anode will be able to go to 4,000mAh; however, the specific power and the cycle life may be compromised. The secret of NMC lies in combining nickel and manganese. An analogy of this is table salt, in which the main ingredients of sodium and chloride are toxic on their own but mixing them serves as seasoning salt and food preserver. Nickel is known for its high specific energy but low stability; manganese has the benefit of forming a spinel structure to achieve very low internal resistance but offers a low specific energy. Combining the metals brings out the best in each. NMC is the battery of choice for power tools and powertrains for vehicles. The cathode combination of one-third nickel, one-third manganese and one-third cobalt offers a unique blend that also lowers raw material cost due to reduced cobalt content. Striking the right balance is important and manufacturers keep their recipes a well-guarded secret. Figure 7 demonstrates the characteristics of the NMC.

Figure 7: Snapshot of NMC NMC has good overall performance and excels on specific energy. This battery is the preferred candidate for the electric vehicle and has the lowest self-heating rate. Courtesy of BCG research

Lithium Nickel Cobalt Aluminum Oxide (LiNiCoAlO2)

The Lithium Nickel Cobalt Aluminum Oxide battery, or NCA, is less commonly used in the consumer market; however, high specific energy and power densities, as well as a long life span, get the attention of the automotive industry. Less flattering are safety and cost. Figure 8 demonstrates the strong points against areas for further development.

Figure 8: Snapshot of NCA High energy and power densities, as well as good life span, make the NCA a candidate for EV powertrains. High cost and marginal safety are negatives. Courtesy of BCG research

Lithium Titanate (Li4Ti5O12)

Batteries with lithium titanate anodes have been known since the 1980s. Li-titanate replaces the graphite in the anode of a typical lithium-ion battery and the material forms into a spinel structure. Li-titanate has a nominal cell voltage of 2.40V, can be fastcharged and delivers a high discharge current of 10C, or 10 times the rated capacity. The cycle count is said to be higher than that of a regular Li-ion; the battery is safe, has excellent low-temperature discharge characteristics and obtains a capacity of 80 percent at 30C (22F). At 65Wh/kg, the specific energy is low. Li-titanate charges to 2.80V/cell, and the end of discharge is 1.80V/cell. Figure 9 illustrates the characteristics of the Li-titanate battery.

Figure 9: Snapshot of Li-titanate Li-titanate excels in safety, lowtemperature performance and life span. Efforts are being made to improve the specific energy and lower cost. Courtesy of BCG research Figure 10 compares the specific energy of lead, nickel- and lithium-based systems. While Li-cobalt is the clear winner by being able to store more capacity than other systems, this only applies to specific energy. In terms of specific power (load characteristics) and thermal stability, Li-manganese and Li-phosphate are superior. As we move towards electric powertrains, safety and cycle life will become more important than capacity.

Figure 10: Typical energy densities of lead, nickel- and lithium-based batteries Lithium-cobalt enjoys the highest specific energy; however, manganese and phosphate are superior in terms of specific power and thermal stability. Courtesy of Cadex

Li-polymer Battery: Substance or Hype?

The polymer hype of the early 2000s is still going strong, however, most users cannot distinguish between a regular Li-ion and one with polymer architecture. Lithiumpolymer differs from other battery systems in the type of electrolyte used. The original

polymer design dating back to the 1970s uses a solid (dry) polymer electrolyte that resembles a plastic-like film. This insulator allows the exchange of ions (electrically charged atoms) and replaces the traditional porous separator that is soaked with electrolyte. A solid polymer has a poor conductivity at room temperature and the battery must be heated to 5060C (122140F) to enable current flow.The much anticipated true plastic battery promised in the early 2000s did not materialize; the conductivity could not be attained at ambient temperature. To make the modern Li-polymer battery conductive at room temperature, gelled electrolyte is added. All Li-ion polymer cells today incorporate a micro porous separator with moisture. The correct term is Lithium-ion polymer (Li-ion polymer or Lipolymer for short). Li-polymer can be built on many systems, such as Li-cobalt, NMC, Li-phosphate and Li-manganese. For this reason, Li-polymer is not considered a unique battery chemistry. Most Li-polymer packs for the consumer market are based on Licobalt. With gelled electrolyte added, what then is the difference between a normal Li-ion and Li-ion polymer? As far as the user is concerned, the lithium polymer is essentially the same as the lithium-ion battery. Both use identical cathode and anode material and contain a similar amount of electrolyte. Although the characteristics and performance of the two systems are alike, the Li-polymer is unique in that a micro porous electrolyte replaces the traditional porous separator. The gelled electrolyte becomes the catalyst that enhances the electrical conductivity. Li-polymer offers slightly higher specific energy and can be made thinner than conventional Li-ion, but the manufacturing cost increases by 1030 percent. Despite the cost disadvantage, the market share of Lipolymer is growing. Li-polymer cells also come in a flexible foil-type case (polymer laminate or pouch cell) that resembles a food package. While a standard Li-ion needs a rigid case to press the electrodes together, Li-polymer uses laminated sheets that do not need compression. A foil-type enclosure reduces the weight by more than 20 percent over the classic hard shell. Furthermore, thin film technology liberates the format design and the battery can be made into any shape, fitting neatly into stylish cell phones and laptops to make them smaller, thinner and lighter. Li-polymer can be made very slim to resemble a credit card. Read about the Pouch Cell. Charge and discharge characteristics of Li-polymer are identical to other Li-ion systems and do not require a special charger. Safety issues are also similar in that protection circuits are needed. Gas buildup during charge can cause some Li-polymer in a foil package to swell, and equipment manufacturers must make allowances for expansion. Li-polymer in a foil package may be less durable than Li-ion in the cylindrical package. Li-polymer is not limited to a foil package and can also be made into a cylindrical design.

Cycle Performance
As part of ongoing research to examine performance degradation caused by cycling, Cadex tested a large volume of portable batteries for wireless communication devices. The population consists of nickel-cadmium, nickel-metal-hydride and lithium-ion. The batteries were prepared by applying an initial charge, followed by a regime of full discharge/charge cycles. The internal

resistance was measured with OhmTest and the self-discharge was obtained from time to time by reading the capacity loss incurred during a 48-hour rest period. The tests were carried out on the Cadex 7000 Seriesbattery analyzers.

Nickel-cadmium
In terms of life cycling, nickel-cadmium is the most enduring battery. Figure 1 illustrates the capacity, internal resistance and self-discharge of a 7.2V, 900mA pack with standard NiCd cells. Due to time constraints, the test was terminated after 2,300 cycles. The capacity remained steady; the internal resistance stayed low at 75mWand the self-discharge was stable. This battery receives a grade A rating for almost perfect performance.

Figure 1: Performance of standard NiCd (7.2V, 900mAh) This battery receives an A rating for a stable capacity, low internal resistance and moderate self-discharge over many cycles. Courtesy of Cadex The ultra-high-capacity nickel-cadmium offers up to 60 percent higher specific energy compared to the standard version, however, this comes at the expense of reduced cycle life. In Figure 2 we observe a steady drop of capacity during 2,000 cycles, a slight increase in internal resistance and a rise in self-discharge after 1,000 cycles.

Figure 2: Performance of ultra-high-capacity NiCd (6V, 700mAh) This battery offers higher specific energy than the standard version at the expense of reducedcycle life. Courtesy of Cadex

Nickel-metal-hydride
Figure 3 examines NiMH, a battery that offers high specific energy at a reasonably low cost. We observe good performance at first but past the 300-cycle mark, the capacity starts to drift downwards rapidly. One can detect a swift increase in internal resistance and self-discharge after cycle count 700. NiMH has a higher specific energy than nickel-cadmium and does not contain toxic metals. The test battery was an older generation; new NiMH performs better.

Figure 3: Performance of NiMH (6V, 950mAh) This battery offers good performance at first but past 300 cycles, the capacity, internal resistance and self-discharge start to increase rapidly. Newer NiMH has better results. Courtesy of Cadex

Lithium-ion
Figure 4 examines the capacity and internal resistance of lithium-ion. We observe a gentle and predictable capacity drop over 1,000 cycles while the internal resistance increases only slightly. Because of low readings, we omit self-discharge. Lithium-ion offers the highest specific energy among the above-mentioned chemistries, contains little or no toxic metals, but needs protection circuits to ensure safe operation. Li-ion is also more expensive to manufacture than the nickelbased equivalent. Batteries tested in a laboratory environment tend to give better results than when used in the field; elements of stress in everyday use do not transfer well into the laboratory. Aging plays a minimal role in a lab because the batteries are cycled over a period of a few months rather than the expected service life of a few years. The temperature is often moderate and the batteries are charged with proper charge equipment, an advantage that the field cannot always claim.

Figure 4: Performance of lithium-ion (3.6V, 500mA) Lithium-ion offers good capacity and steady internal resistance over 1,000 cycles. Self-discharge was omitted because of low readings Courtesy of Cadex The load signature of the discharge plays an important role when testing batteries, and our laboratory batteries were discharged with an even DC load. Cellular phones and other digital devices draw pulsed loads that stress the battery more than with DC. One could argue, however, that the lab tests apply a full discharge whereas the field user discharges the battery to about 80 percent. The degradation of a battery receiving a 100 percent discharge with a DC load may not be the same as an 80 percent discharge on a pulsed load, and we keep this possible discrepancy in mind when studying the results.

The tests were done with batteries from an earlier generation. Newer models show improved results, and this is especially apparent with NiMH. The internal resistance of the modern NiMH is similar to NiCd, so is the cycle life. The Li-ion battery tested was Li-cobalt for cellular phones. We excluded lead acid from the test because this battery is seldom used for portable applications. Lead acid is heavy and does not cycle well, especially on full discharges. The outcome of battery tests depends very much on the application for which the battery is designed, and we distinguish between consumer and industrial use. With the advent of the electric powertrain, a new category of batteries is emerging. Built for safety and longevity, these batteries have a specific energy that is typically only one-half that of consumer batteries.

Supercapacitor
The supercapacitor, also known as ultracapacitor or double-layer capacitor, differs from a regular capacitor in that it has a very high capacitance. A capacitor stores energy by means of a static charge as opposed to an electrochemical reaction. Applying a voltage differential on the positive and negative plates charges the capacitor. This is similar to the buildup of electrical charge when walking on a carpet. Touching an object releases the energy through the finger. We group capacitors into three family types and the most basic is the electrostatic capacitor, with a dry separator. This capacitor has a very low capacitance and is used to filter signals and tune radio frequencies. The size ranges from a few pico-farad (pf) to low microfarad (uF). The next member is the electrolytic capacitor, which is used for power filtering, buffering and coupling. Rated in microfarads (uF), this capacitor has several thousand times the storage capacity of the electrostatic capacitor and uses a moist separator. The third type is the supercapacitor, rated in farads, which is again thousands of times higher than the electrolytic capacitor. The supercapacitor is ideal for energy storage that undergoes frequent charge and discharge cycles at high current and short duration. Faradis a unit of capacitance named after the English physicist Michael Faraday. One farad stores one coulomb of electrical charge when applying one volt. One microfaradis one million times smaller than a farad, and one pico-farad is again one million times smaller than the microfarad. Engineers at General Electric first experimented with the electric double-layer capacitor, which led to the development of an early type of supercapacitor in 1957. There were no known commercial applications then. In 1966, Standard Oil rediscovered the effect of the double-layer capacitor by accident while working on experimental fuel cell designs. The company did not commercialize the invention but licensed it to NEC, which in 1978 marketed the technology as supercapacitor for computer memory backup. It was not until the 1990s that advances in materials and manufacturing methods led to improved performance and lower cost. The modern supercapacitor is not a battery per se but crosses the boundary into battery technology by using special electrodes and electrolyte. Several types of electrodes have been tried and we focuse on the double-layer capacitor (DLC) concept. It is carbon-based, has an organic electrolyte that is easy to manufacture and is the most common system in use today. All capacitors have voltage limits. While the electrostatic capacitor can be made to withstand high volts, the supercapacitor is confined to 2.52.7V. Voltages of 2.8V and higher are possible but they would reduce the service life. To achieve higher voltages, several supercapacitors are connected in series. This has disadvantages. Serial connection reduces the total capacitance, and strings of more than three capacitors require voltage balancing to prevent any cell from going into over-voltage. This is similar to the protection circuit in lithium-ion batteries. The specific energy of the supercapacitor is low and ranges from 1 to 30Wh/kg. Although high compared to a regular capacitor, 30Wh/kg is one-fifth that of a consumer Li-ion battery. The discharge curve is another disadvantage. Whereas the electrochemical battery delivers a

steady voltage in the usable power band, the voltage of the supercapacitor decreases on a linear scale from full to zero voltage. This reduces the usable power spectrum and much of the stored energy is left behind. Consider the following example. Take a 6V power source that is allowed to discharge to 4.5V before the equipment cuts off. With the linear discharge, the supercapacitor reaches this voltage threshold within the first quarter of the cycle and the remaining three-quarters of the energy reserve become unusable. A DC-toDC converter could utilize some of the residual energy, but this would add to the cost and introduce a 10 to 15 percent energy loss. A battery with a flat discharge curve, on the other hand, would deliver 90 to 95 percent of its energy reserve before reaching the voltage threshold. Table 1 compares the supercapacitor with a typical Li-ion.

Function Charge time Cycle life Cell voltage Specific energy (Wh/kg) Specific power (W/kg) Cost per Wh Service life (in vehicle) Charge temperature Discharge temperature

Supercapacitor 110 seconds 1 million or 30,000h 2.3 to 2.75V 5 (typical) Up to 10,000 $20(typical) 10 to 15 years 40 to 65 (40 to 149 C F) 40 to 65 (40 to 149 C F)

Lithium-ion (general) 1060 minutes 500 and higher 3.6 to 3.7V 100200 1,000 to 3,000 $2 (typical) 5 to 10 years 0 to 45 (32 113 C to F) 20 to 60 (4 to 140 C F)

Table 1: Performance comparison between supercapacitor and Li-ion Courtesy of Maxwell Technologies, Inc. Rather than operating as a stand-alone energy storage device, supercapacitors work well as low-maintenance memory backup to bridge short power interruptions. Supercapacitors have also made critical inroads into electric powertrains. The virtue of ultra-rapid charging and delivery of high current on demand makes the supercapacitor an ideal candidate as a peak-load enhancer for hybrid vehicles, as well as fuel cell applications. The charge time of a supercapacitor is about 10 seconds. The charge characteristic is similar to an electrochemical battery and the charge current is, to a large extent, limited by the charger. The initial charge can be made very fast, and the topping charge will take extra time. Provision must be made to limit the initial current inrush when charging an empty supercapacitor. The supercapacitor cannot go into overcharge and does not require full-charge detection; the current simply stops flowing when the capacitor is full. The supercapacitor can be charged and discharged virtually an unlimited number of times. Unlike the electrochemical battery, which has a defined cycle life, there is little wear and tear by cycling a supercapacitor. Nor does age affect the device, as it would a battery. Under normal conditions, a supercapacitor fades from the original 100 percent capacity to 80 percent in 10 years. Applying higher voltages than specified shortens the life. The supercapacitor functions well at hot and cold temperatures.

The self-discharge of a supercapacitor is substantially higher than that of an electrostatic capacitor and somewhat higher than the electrochemical battery. The organic electrolyte contributes to this. The stored energy of a supercapacitor decreases from 100 to 50 percent in 30 to 40 days. A nickel-based battery self-discharges 10 to 15 percent per month. Li-ion discharges only five percent per month. Supercapacitors are expensive in terms of cost per watt. Some design engineers argue that the money for the supercapacitor would better be spent on a larger battery. We need to realize that the supercapacitor and chemical battery are not in competition; rather they are different products serving unique applications.Table 2 summarizes the advantages and limitations of the supercapacitor.

Virtually unlimited cycle life; can be cycled millions of time High specific power; low resistance enables high load currents Charges in seconds; no end-of-charge termination required Advantages Simple charging; draws only what it needs; not subject to overcharge Safe; forgiving if abused Excellent low-temperature charge and discharge performance Low specific energy; holds a fraction of a regular battery Linear discharge voltage prevents using the full energy spectrum Limitations High self-discharge; higher than most batteries Low cell voltage; requires serial connections with voltage balancing High cost per watt Table 2: Advantages and limitations of supercapacitors

Fuel Cell Technology

A fuel cell is an electrochemical device that combines hydrogen fuel with oxygen to produce electricity, heat and water. The fuel cell is similar to a battery in that an electrochemical reaction takes place as long as fuel is available. The hydrogen fuel is stored in a pressurized container and oxygen is taken from the air. Because of the absence of a burning process, there are no harmful emissions, and the only by-product is pure water. Fundamentally, a fuel cell is electrolysis in reverse, using two electrodes separated by an electrolyte. The anode (negative electrode) receives the hydrogen and the cathode (positive electrode) collects the oxygen. A catalyst at the anode separates hydrogen into positively charged hydrogen ions and electrons; the oxygen is ionized and migrates across the electrolyte to the anodic compartment, where it combines with hydrogen. A

single fuel cell produces 0.60.8V under load. To obtain higher voltages, several cells are connected in series. Figure 1 illustrates the concept of a fuel cell.

Figure 1: Concept of a fuel cell The anode (negative electrode) receives the hydrogen and the cathode (positive electrode) collects the oxygen.
Source: US Department of Energy, Office of Energy Efficiency and Renewable Energy

Fuel cell technology is twice as efficient as combustion in turning carbon fuel to energy. Hydrogen, the simplest chemical element (one proton and one electron), is plentiful and exceptionally clean as a fuel. Hydrogen makes up 90 percent of the universe and is the third most abundant element on the earths surface. Such a wealth of fuel would provide an almost unlimited pool of clean energy at relatively low cost. But there is a hitch. Hydrogen is usually bound to other substances and unleashing the gas takes technology and a substantial amount of energy. In terms of net calorific value (NCV), hydrogen is more costly to produce than gasoline. Some say that hydrogen is nearly energy neutral, meaning that it takes as much energy to produce as it delivers at the end destination. Read more about Batteries Against Fossil Fuel. Storage of hydrogen poses a further disadvantage. Pressurized hydrogen requires heavy steel tanks, and the NCV by volume is about 24-times lower than a liquid petroleum product. In liquid form, which is much denser, hydrogen needs extensive insulation for cold storage. Hydrogen can also be produced with a reformer by means of extraction from an existing fuel, such as methanol, propane, butane or natural gas. Converting these fossil fuels into pure hydrogen releases some leftover carbon, but this is 90 percent less harmful than what comes from the tailpipe of a car. Carrying a reformer would add weight to the vehicle and increase its cost. Reformers are also known to be sluggish. The net benefit of hydrogen conversion is in question because it does not solve the energy problem. With the availability of hydrogen through extraction, the fuel cell core (stack) to convert hydrogen and oxygen to electricity is expensive and the stack has a limited life span. Burning fossil fuels in a combustion engine is the simplest and most effective means of harnessing energy, but this contributes to pollution.

Sir William Grove, a Welsh judge and gentleman scientist, developed the fuel cell concept in 1839, but the invention never took off. This was in part due to the rapidly advancing internal combustion engine, which promised better results. It was not until the 1960s that the fuel cell was put to practical use during the Gemini space program. NASA preferred this clean power source to nuclear or solar power. The alkaline fuel cell system generated electricity and produced the drinking water for the astronauts. High material costs made the fuel cell prohibitive for commercial use at that time. This did not hinder Karl Kordesch, the co-inventor of the alkaline battery, from converting his cars power source to an alkaline fuel cell in the early 1970s. Kordesch drove his car for many years in Ohio, USA. He placed the hydrogen tank on the roof and utilized the trunk to place the fuel cell as well as backup batteries. According to Kordesch, there was enough room for four people and a dog. The 1990s brought renewed interest in the fuel cell; however, this enthusiasm started to diminish again in the 21st century. Just as there are different battery chemistries, so also are there several fuel cell systems to choose from. Lets look at the most common types and examine the applications.

Proton Exchange Membrane Fuel Cell(PEMFC)

The proton exchange membrane, also known as PEM, uses a polymer electrolyte. PEM is one of the furthest developed and most commonly used fuel cell systems; it powers cars, serves as a portable power source and provides backup power in lieu of stationary batteries in offices. The PEM system allows compact design and achieves a high energy-to-weight ratio. Another advantage is a relatively quick start-up when applying hydrogen. The stack runs at a moderate temperature of 80C (176F) and has an efficiency of 50 percent. (In comparison, the internal combustion engine is only about 25 percent efficient.) The limitations of the PEM fuel cell are high manufacturing costs and complex water management systems. The stack contains hydrogen, oxygen and water. If dry, water must be added to get the system going; too much water causes flooding. The system requires pure hydrogen; lower fuel grades can cause decomposition and clogging of the membrane. Testing and repairing a stack is difficult, given that a 150V, 50kW stack to power a small car requires 250 cells. Extreme operating temperatures are a further challenge. Freezing water can damage the stack, and the manufacturer recommends heating elements to prevent ice formation. When the fuel cell is cold, start-up is slow and the performance is poor at first. Excessive heat can also cause damage. Controlling the operating temperatures as well as supplying enough oxygen requires compressors, pumps and other accessories that consume about 30 percent of the energy generated. If operated in a vehicle, the PEMFC stack has an estimated service life of 2,000-4,000 hours. Start-and-stop conditions induce drying and wetting that contribute to membrane stress. Running continuously, the stationary stack is good for about 40,000 hours. Stack replacement is a major expense.

Alkaline Fuel Cell(AFC)

The alkaline fuel cell has become the preferred technologyfor aerospace, including the space shuttle. Manufacturing and operating costs are low, especially for the stack. While the separator for the PEM costs between $800 and $1,100 per square meter, the same material for the alkaline system is almost negligible. (The separator for a lead acid battery costs $5 per square meter.) Water management is simple and does not need compressors and other peripherals. A negative is that AFC is larger in physical size than the PEM and needs pure oxygen and hydrogen as fuels. Carbon dioxide in a polluted city can poison the stack.

Solid Oxide Fuel Cell (SOFC)

Electric utilities use three types of fuel cells, which are molten carbonate, phosphoric acid and solid oxide fuel cells. Among these choices, the solid oxide (SOFC) is the least developed but has received renewed attention because of breakthroughs in cell material and stack design. Rather than operating at the very high operating temperature of 800 1,000C (1,4721,832F), a new generation of ceramic material has brought the core down to a more manageable 500600C (9321,112F). This allows the use of conventional stainless steel rather than expensive ceramics for auxiliary parts. High temperature allows direct extraction of hydrogen from natural gas through a catalytic reforming process. Carbon monoxide, a contaminant for the PEM, is a fuel for the SOFC. Being able to accept carbon-based fuels without a designated reformer and delivering high efficiency pose significant advantages for this type of fuel cell. Cogeneration by running steam generators from the heat by-product raises the SOFC to 60 percent efficiency, one of the highest among fuel cells. As a negative, high stack temperatures require exotic materials for the core that add to manufacturing costs, lower longevity and decrease reliability. With the newer SOFC systems operating at lower temperatures, however, this drawback has been reduced.

Direct Methanol Fuel Cell (DMFC)

During the past years, portable fuel cells, also known as miniature or micro fuel cells, have gained public attention, and the most promising development is the direct methanol fuel cell. This small fuel cell is inexpensive to manufacture, convenient to use and does not require pressurized hydrogen gas. DMFC provides a reasonably good electrochemical performance, and charging occurs by simply replacing the fuel cartridge. This enables continued operation without downtime. Fuel cells with liquid fuels (ethanol or methanol) have a further advantage over hydrogen in the automotive market in that the fuel can be transported, stored and dispensed with known technologies. Hydrogen, on the other hand, exhibits safety risks, storage problems and needs large investments in special pipelines. Read about the miniature fuel cell. Table 3 describes the applications and summarizes the advantages and limitations of common fuel cells. For completeness of listing, the table also includes the Molten Carbonate (MCFC) and Phosphoric Acid (PAFC), two varieties not described in the text above. These two fuel cell versions have been around for a long time also but have

received less publicity than the others.

Type of Fuel Cell Proton Exchange Membrane (PEMFC)

Applications Medium to large systems for portable, stationary and automotive

Advantages Compact design; long operating life; offers quick start-up, 50% efficient Low manufacturing, operation costs; no compressor; fast cathode kinetics Efficient; cogeneration utilizes heat to run turbines Lenient to fuels; for cogeneration Lenient to fuels; uses natural gas; 60% efficient with cogeneration Compact; feeds directly off methanol; no compressor

Limitations Expensive to build; needs pure hydrogen; complex heat and water management. Large size; needs pure hydrogen and oxygen Electrolyte instability; limited service life

Status

Practical and most widely developed

Alkaline (AFC)

Space (NASA), terrestrial transport, submarines

New interest due to low manufacturing, operating costs Well developed; semicommercial

Molten Carbonate (MCFC) Phosphoric Acid (PAFC)

Large-scale power generation Medium to large power generation

Low efficiency; limited service In competition life; expensive with PEMFC catalyst High temperatures; exotic metals; high manufacturing costs; short life New material, stack design sets off renewed development

Solid Oxide (SOFC)

Medium to large power generation

Direct Methanol (DMFC)

Portable, mobile and stationary use

Complex stack; Liquid fuels are slow load easier to handle response; 20% than hydrogen efficient

Table 3: Advantages and disadvantages of various fuel cell systems The development of the fuel cell has not advanced at the same pace as batteries; a direct battery replacement is not yet feasible.

Developments
In spite of environmental benefits, the fuel cell requires extensive development before it can compete in industrial and consumer markets. The existing problems revolve around slow start-up times, low power output, sluggish response on power demand, poor

loading capabilities, narrow power bandwidth, short service life and high cost. These negative traits are especially noticeable for the direct methanol fuel cell. Similar to batteries, the performance of all fuel cells degrades with age, and the stack gradually loses efficiency. The relatively high internal resistance of full cells poses a challenge. Each cell of a stack produces about one volt when in open-circuit condition, and a heavy load causes a notable voltage drop. Figure 4 illustrates the voltage and power bandwidth as a function of load.

Figure 4: Power band of a portable fuel cell High internal resistance causes the cell voltage to drop rapidly with load. The power band is limited to between 300 and 800mA.
Courtesy of Cadex

Fuel cells operate best at a 30 percent load factor; higher loads reduce efficiency. A load factor approaching 100 percent, as is common with a battery, is not practical with the fuel cell. In addition, the fuel cell has poor response characteristics and takes a few seconds to react to power demands. Rather than acting as a stand-alone engine, as the developers had hoped, the fuel cell works as a support function by giving the battery the master status. The fuel cell becomes a slave providing the charge duty. This relationship enables both parties to deliver continuous service. Having failed in the automotive field, fuel cell manufacturers explore new applications. Large 40,000kW fuel cells are being built to generate electricity in remote locations. Fuel cells also replace battery banks and diesel generators in office buildings, as they can be installed in tight storage places and on rooftops with minimal maintenance. Forklifts running non-stop are further candidates for fuel cell technology, which allows continuous, pollution-free operation.

Paradox of the Fuel Cell

The fuel cell enjoyed the height of popularity in the 1990s, when scientists and stock promoters envisioned a world run on a clean and inexhaustible resource hydrogen. They predicted that cars would run on fuel cells and households would generate electricity from back-yard fuel cells. The stock prices skyrocketed, and it took a few years before marginal performance, high manufacturing costs and short service life brought the hydrogen dream down. Hype and investment funding have since moderated,

and it is hoped that a more sensible approach will eventually find the proper use for the fuel cell. It had been said that the fuel cell would transform the world as the microprocessor did. Experts further claimed that using an inexhaustible source of fuel, hydrogen, would improve the quality of life, and the environmental consequences of burning fossil fuels would be solved forever. From 1999 through 2001, more than 2,000 organizations were actively involved in fuel cell development, and four of the largest public fuel cell companies in North American raised over a billion dollars in public stock offerings. What went wrong? Hydrogen is not a source of energy per se. We must look at it as a medium to transport and store energy. When envisioning burning an endless supply of hydrogen, we need to first produce the resource because hydrogen is not available abundantly in the earth, ready to burn, as oil and natural gas are. To retrieve the hydrogen for fuel, we need energy to convert the resource into a usable product in a similar way as we use electricity to charge a flat battery. If electricity produces hydrogen, then this energy source should come from a renewable resource. This is often not the case; much of our current energy comes from burning coal, oil and natural gas. Fossil fuel lends itself well to producing hydrogen, but taking this valuable fuel to unleash hydrogen does not make much sense when it costs as much or more for extraction than burning it directly. It is conceivable that the fuel cell will never become the engine that scientists had hoped, just as the attempt to fly airplanes on steam failed in the mid 1800s. Hydrogen is, however, being used to propel satellites and space vehicles into orbit. Liquid hydrogen has the highest energy-to-mass ratio; but the specific energy by volume reveals a truer picture when considering storage and delivery for terrestrial use. Gasoline has almost 24 times the specific energy of pure hydrogen by volume. Is there hope for the fuel cell? Many hope it will succeed. Taxpayers may one day need to subsidize this clean energy source similar to subsidizing the electric car. Furthermore, governments may mandate its use for environmental reasons or as an alternative for the dwindling fossil fuels. Wehope that the development of fuel cells will eventually succeed in finding a replacement for the polluting internal combustion engine.

The Miniature Fuel Cell

For a long time, manufacturers explored ways to replace the electrochemical battery. Higher energy densities, smaller size, lower cost per watt and faster charging times are on the wish list. Electrical energy from rechargeable batteries is expensive when considering the high purchase price, the limited life span and the limited power this portable source can deliver. Read more about Batteries against Fossil Fuel.

Will the fuel cell replace the battery?

Since the invention in 1839 by Sir William Grove, the fuel cell

remained a scientific oddity. It was only in the 1950s that this power generator was used for the first time as part of US space and military programs. In the 1980s, the fuel cell had another rebirth when scientists and stock promoters envisioned a world powered by a clean power source fed by an inexhaustible fuel, hydrogen. They forecasted cars running by fuel cells and households deriving electrical power from back-yard fuel cell units. In the late 1990s, fuel cell technology gained hype status and many saw this power source as the gateway to the future. High manufacturing costs and short service life were in the way to make this dream a reality. The fuel cell uses hydrogen and oxygen as fuel. Combining the two gases generates electricity and water. There is not combustion and no pollution. The byproduct is pure water. The system runs so clean that Ballard, a developer of fuel cell stacks, offered the guests tea from the hot water produced by the fuel cell. The absence of exhaust fumes enables running a fuel cell in an enclosed room, such as an office of living room. The theoretical energy output of the fuel cell is high, but over half is lost in heat. During the past years, portable versions of the fuel cells have emerged. The most promising miniature fuel cell is the direct methanol fuel cell. Read more about Fuel Cell Technology. DMCF is inexpensive, convenient, does not require pressurized hydrogen gas and provides a reasonably good electrochemical performance. Current systems produce 900Wh of power and offer an energy density of 102Wh/l, but this volumetric dimension is still large compared to a lithium-ion battery. Charging consists by replacing the cartridge on the fly. This provides a continued source of energy, similar to fueling a car. Figure 1 shows a miniature Toshiba fuel cell, also known as micro fuel cell; Figure 2 demonstrates refueling with methanol that is 99.5 percent pure.

Figure 1: Micro fuel cell. This prototype Figure 2: Toshiba fuel cell micro fuel cell is capable of providing with refueling cartridge. The 300mW of continuous power. fuel in a 10ml tank is 99.5 percent pure methanol. Courtesy of Toshiba Courtesy of Toshiba Manufactures of micro fuel cells admit that a direct battery replacement with high power, small size and competitive price is still several years away. Rather than offering an outright battery replacement, todays micro fuel cell

serves as a charger to provide continuous operation for the onboard battery. Miniature fuel cells are still in development and the reasons are multifold. A typical micro fuel cell has an output of 300mW and can only supply enough power to keep a cell phone battery charged. A laptop consuming 30 watts would need 100 miniature fuel cells to sustain continuous operation. Furthermore, transportation authorities prohibit passengers from carrying bottled fuel on an aircraft, a rule that might soon change. The Dangerous Goods Panel (DGP) of the International Civil Aviation Organization (ICAO) has already made an exclusion to allow the transport and operation of methanol fuel cells on commercial flights. This provision does not yet extend to bottled hydrogen. Improvements are being made, and Toshiba unveiled prototype fuel cells for laptops and other applications generating 20 to 100 watts of power. At 100 Wh/l, the units are compact and the specific energy is comparable with a NiCd battery. (I appreciate the honesty of Japanese manufacturers in describing the technology as being in its infancy.) Toshiba has given no indication as to when the product could be commercially available. Meanwhile, Panasonic claims to have doubled the power output from 10 watts to 20 watts with similar size. Panasonic specifies a calendar life of 5,000 hours if the fuel cell is used intermittently for eight hours per day. Durability had been standing in the way of commercializing its use. Angstrom Power is developing a portable fuel cell that runs on stored hydrogen and takes oxygen from the air. The system has no pump and fan and is totally silent. Increased efficiency and smaller size are the advantages of pure hydrogen over methanol. The aim is to offer a power source that is clean, quiet and can be refueled on the fly. Similar applications are possible for cellular phones. Figure 3 illustrates an application as a bicycle lamp. Figure 3: Fuel cell powered bicycle lamp. The 21cc cartridge provides the equivalent energy of about 10 AA disposable alkaline batteries. The only by-product is water vapor. The runtime between refueling is 20 hours. Courtesy of Angstrom Power According to Angstrom Power, the micro hydrogen bike lights have delivered good performance in winter and spring conditions and the user feedback is positive. The hydrogen fuel is stored in a 21cc cartridge and provides the equivalent energy of about 10 AA disposable alkaline batteries. The only by-product is water vapor. Refueling takes a few minutes and provides a continuous runtime of about 20 hours.

Current draw is not critical on a small bicycle light, especially when using low-drain LED technology. A laptop, on the other hand, requires about 40 watts of power, and a small fuel cell cannot provide enough output to sustain the demand. The system needs a battery as back up. In essence, the fuel cell becomes a slave to the battery and serves in the capacity of a charger. The same scenario applies to fuel cell-powered cell phones and cameras. Military and recreational users are also experimenting with the miniature fuel cell. Figure 4 illustrates a portable fuel cell made by SFC Smart Fuel Cell. The EFOY fuel cell comes in different capacities that ranges from 600 to 2160 watt hours per day. Figure 4: Portable fuel cell for consumer market The fuel cell converts hydrogen and oxygen to electricity and clean water is the only byproduct. Fuel cells can be used indoors as an electricity generator. Courtesy of SFC Smart Fuel Cell AG (2010) As good as the fuel cell may look from the outside, the product leaves many unresolved problems that prevent broad consumer acceptance. One of the drawbacks is a slow start-up, and another is the low electrochemical activity at the anode. This is especially apparent with the DMCF. Each cell produces about one volt and when loaded, the relatively high internal resistance causes the voltage drops quickly. The inherent limited power bandwidth causes this phenomenon. A third weakness is the relatively short life span. The capacity may be high when new but the output begins to fade with use similar to an aging battery. One of the inhibiting factors is the gradual rise of internal resistance, which limits applications drawing heavy load currents. High device and operating costs are another disadvantages. Read more about Fuel Cell Technology.

It is regretful that the fuel cell has not enjoyed the same breakthroughs as microelectronics. The Moores law does not apply here. When examining alternative power sources to the struggling fuel cell, the traditional battery begins to look surprisingly good. A battery pack is small, clean, quiet, and provides an instant source of high power on demand, even at cold temperatures. It is our hope, however, that the fuel cell will eventually succeed as a clean energy source to extend the range of portable power and reduce pollution.

Alternate Battery Systems

The media tells us of wonderful new batteries being developed that promise long runtimes and are paper-thin, durable, cheap and environmental friendly. While these experimental packs may be able to produce a voltage, the downsides are seldom revealed. The typical shortcomings are weak load capabilities and short cycle life. Yes, even a lemon can be made into a battery. Just poke a copper coin and galvanized nail into the innards. The power is low and you need 500 lemons to light a flashlight bulb. Using seawater as electrolyte has also been tried. The sea would produce an endless supply of electricity, but the retrieved energy is only good to light a flashlight and corrosion buildup limits the service life. Outside the much-talked-about lead, nickeland lithium-based batteries, other systems show promise. Lets have a closer look at them in roughly the sequence of age.

Nickel-iron
After inventing nickel-cadmium in 1899, Swedens Waldemar Jungner tried to substitute iron for cadmium to save money; however, poor charge efficiency and gassing (hydrogen formation) prompted him to abandon the development without securing a patent. In 1901, Thomas Edison continued the development of the nickel-iron battery as a substitute to lead acid for electric vehicles. He claimed nickel-iron was far superior to batteries using lead plates and acid and counted on the emerging electric vehicle market. He lost out when gasoline-powered cars took over and was deeply disappointed when the auto industry did not adopt nickel-iron as the starter, lighting and ignition battery (SLI) for cars. The nickel-iron battery (NiFe) uses an oxide-hydroxide cathode and an iron anode with potassium hydroxide electrolyte and produces a nominal cell voltage of 1.2V. NiFe is resilient to overcharge and over-discharge and can last for more than 20 years in standby applications. Resistance to vibrations and high temperatures made NiFe the preferred battery for mining in Europe, and during World War II the battery powered the German V-1 flying bomb and the V-2 rockets. Other applications are railroad signaling, forklifts, and power for stationary applications. NiFe has a low specific energy of about 50Wh/kg, has poor low-temperature performance and exhibits high self-discharge of 20 to 40 percent a month. This, with high manufacturing cost, prompted the industry to stay faithful to lead acid.

Nickel-zinc
Nickel-zinc batteries are similar to nickel-cadmium in that they use an alkaline electrolyte and a nickel electrode, but differ in voltage; NiZn provides 1.6V/cell rather than 1.2V, which NiCd delivers. Nickel-zinc was first developed in the 1920s but it suffered from short cycle life caused by dendrite growth. This led to electrical shorting. Improvements in the electrolyte have reduced this problem, and NiZn is being considered again for commercial uses. Low cost, high power output and good

temperature operating range make this chemistry attractive. NiZn charges at a constant current to 1.9V/cell and cannot take trickle charge. The specific energy is similar to other nickel-based systems. NiZn can by cycled 200300 times, has no heavy toxic materials and can easily be recycled. Some are available in AA cells.

Nickel-hydrogen
When research for nickel-metal-hydride began in 1967, problems with metal instabilities caused a shift towards the development of the nickel-hydrogenbattery (NiH). NiH uses a steel canister to store the hydrogen gases at a pressure of 1,200psi (8,270kPa). The cell includes solid nickel electrodes, hydrogen electrodes, gas screens and electrolyte. These components are encapsulated in the pressurized vessel. NiH has a nominal cell voltage of 1.25V and the specific energy is 4075Wh/kg. The advantages are long service life even with full discharge cycles, good calendar life due to low corrosion, minimal self-discharge, and a remarkable temperature performance of 28C to 54C (20F to 130F). These attributes make NiH ideal for satellite use. Scientists are developing NiH batteries for terrestrial use and hope to supply markets for energy storage systems and the electric vehicle. The negatives are low specific energy and high cost. A single cell for a satellite application costs thousands of dollars.

Zinc-air
Zinc-air batteries generate electrical power by an oxidation process of zinc and oxygen from the air. The cell can produce 1.65V, however, 1.4V and lower achieves a longer lifetime. To activate the battery, the user removes a sealing tab that enables airflow and the battery reaches full operating voltage within five seconds. Once turned on, the battery cannot be reverted back to the standby mode, the chemicals dry out, and the battery has a short shelf life. Adding a tape to stop airflow slows the degeneration. Zinc-air batteries have similarities to the proton exchange membrane fuel cell (PEMFC) in that they use oxygen in the air as fuel for the positive electrode. Read about the fuel cell. Air can, to a certain extent, control the rate of the reaction. Zinc-air is considered a primary battery, however, there are recharging versions for high-power applications. Recharging occurs by replacing the spent zinc electrodes, which can be in the form of a zinc electrolyte paste. Other zinc-air batteries use zinc pellets. At 300400Wh/kg, zinc-air has a high specific energy but the specific power is low. Manufacturing cost is low and in a sealed state, zinc-air has a two percent self-discharge per year. Zinc-air is sensitive to extreme temperatures and high humidity. Pollution also affects performance, and high ambient carbon dioxide reduces the performance by increasing the internal resistance. Typical applications include hearing aids; high-power versions operate remote railway signaling and safety lamps at construction sites.

Silver-zinc
The silver-zinc battery has served a critical role for defense and space applications, as well as TV cameras and other professional equipment needing extra runtime. High cost

and short service life locked the battery out of the commercial market but its on the verge of a rebirth. The zinc electrode and separator were the primary cause of failure in the original design; the zinc electrode degraded rapidly when cycled. The battery developed zinc dendrites that pierced the separator, causing electrical shorts. Furthermore, the separator degraded whether used or not by simply sitting in the potassium hydroxide electrolyte. This limited the calendar life to about two years. Improvements in the zinc electrode and separator promise a longer service life and a 40 percent higher specific energy than Li-ion. Silver-zinc is safe, has no toxic metals and can be recycled, but the use of silver makes the battery expensive to manufacture.

Sodium-sulfur
Sodium batteries, also known as molten salt or thermal battery, come in primary and secondary versions. The battery uses molten salts as an electrolyte and operates at a temperature of 400700C (7521,292F). Newer designs run at a lower 245350C (473662F) temperature. Conceived by the Germans during World War II and used in their V-2 rockets, the electrolyte of the molten salt batteries is inactive when cold and has a long storage of more than 50 years. Once activated with a heat source, the battery can provide a high power burst for a fraction of a second or deliver energy over several hours. The high power is made possible by the good ionic conductivity of the molten salt. Primary sodium batteries are almost exclusively used for the military as a one-shot engagement in guided missiles. However, interest of the reader lies in the rechargeable version. The rechargeable sodium-sulfur (NaS) gained worldwide attention during the 1970s and 1980s, but short service life and high cost dampened the enthusiasm. The sodiumnickel-chloride battery, also known as ZEBRA,* came to the rescue and today this battery is being used successfully in many applications. ZEBRA has a nominal cell voltage of 2.58 volts and an specific energy of 90 120Wh/kg, a level comparable with Li-manganese and Li-phosphate. The service life is about eight years and 3,000 cycles. It can be fast-charged, is non-toxic and the raw materials are abundant and low-cost. ZEBRA batteries come in large sizes of 10kWh or higher and typical applications are forklifts, railways, ships, submarines and electric cars. A growing market for sodium-based batteries is load leveling, also known as grid storage. The Think City EV has a choice of ZEBRA and Li-ion. ZEBRA has advantages when operating at extreme temperatures and when the battery is in continuous use, such as in taxis and delivery vans. The ZEBRA battery must be heated to 270350C (518662F), a temperature that is lower than the original sodium-sulfur battery. Even though special insulation minimizes heat loss, heating consumes 14 percent of the batterys energy per day, which results in a self-discharge of 18 percent. An active ZEBRA battery should be on charge or in use. It takes 34 days to cool down, and reheating takes about two days depending on the SoC at time of shutdown. Common failures include electrical shorts due to corrosion of

the insulators, which then become conductive, as well as growth of dendrites, which increases self-discharge.

Reusable Alkaline
Introduced in 1992, the reusable alkaline serves as an alternative to disposable batteries; however, the anticipated breakthrough never occurred and today the reusable alkaline satisfies only a small market niche. The lack of consumer appeal is regrettable when considering the environmental benefit of having to discard fewer batteries. It is said that the manufacturing cost of the reusable battery is similar to that of a regular alkaline and the ability to recharge, although only for a limited time, offers definite advantages. Recharging alkaline batteries is not new. Ordinary alkaline batteries have been recharged in households for many years, but manufacturers do not endorse this practice for safety reasons. Recharging is only effective if the alkaline is discharged to less than 50 percent before recharging. The number of recharges depends on the depth of discharge and is limited to just a few cycles at best. Each recharge stores less capacity until the battery is finally worn out. There is a cautionary advisory: charging ordinary alkaline batteries may generate hydrogen gas that can lead to explosion. The reusable alkaline overcomes some of these deficiencies, but not all. With each recharge, the battery loses charge acceptance, and the longevity is in direct relationship to the depth of discharge. The deeper the discharge, the fewer cycles the battery can endure. At 50 percent depth of discharge, we can expect 50 cycles. The manufacturer may have overestimated the eagerness of the user wanting to recharge early; most users run a battery empty and recharge when necessary. Tests performed by Cadex on AA reusable alkaline cells show a capacity reading on the first discharge that is similar to that of a regular alkaline. After the first recharge using the manufacturers charger, however, the reusable alkaline settles at only 60 percent, a capacity slightly below that of NiCd. Repeat cycling in the same manner resulted in further capacity losses. The discharge current was 200mA (0.2 C-rate, or one-fifth of the rated capacity) and the end-of-discharge threshold was set to 1V/cell. An additional limitation of the reusable alkaline system is its low permissible load current of 400mA (lower than 400mA provides better results). Although adequate for flashlights and personal entertainment devices, 400mA is insufficient to power most digital cameras and communication devices. Table 1 compares the specific energy, voltage, self-discharge and runtime of over-thecounter batteries. Available in AA, AAA and other sizes, these cells can be used in portable devices designed for these norms. Even though the cell voltages may vary, the end-of-discharge voltages are common, which is typically 1V/cell. Portable devices have some flexibility in terms of voltage range. It is important not to mix and match cells and to always use the same type of batteries in the holder. Safety concerns and voltage incompatibility prevent the sales of lithium-ion batteries in AA and AAA formats.

Runtime Battery type Specific energy Voltage AA cell Self-discharge Capacity after 1 year storage Estimated photos on digital camera 100 shots

Regular alkaline Reusable alkaline Eneloop* NiMH

4,300mWh; non-rechargeable 2,000mWh; lower on subsequent recharge 2,400mWh, rechargeable 2,700mWh, rechargeable

1.5V

95%

1.4V

95%

100 shots

1.2V 1.2V

85% 50%

500 shots 600 shots

Table 1: Comparison of alkaline, reusable alkaline, Eneloop and NiMH * Eneloop is a Sanyo trademark, based on NiMH. Karl Kordesch, professor and co-inventor of the reusable alkaline, expressed disappointment in the market failure of this battery by saying, and I paraphrase, If only people could be taught to recharge the battery sooner, before the energy is fully depleted. The reusable alkaline could indeed provide extended service life if the user discharged the battery by only a small amount before recharging, but this does not suit consumer behavior. A user expects to get the full use of a battery before having to recharge. NiMH has since replaced the reusable alkaline. Price is important and to lower cost for the consumer market, some battery manufacturers have reduced the capacity of the AA cell from 2,700mAh to 2,000mAh. The 2,700mAh AA cell is still available. Manufacturers are well tuned to customer needs and make the necessary adjustments to best serve the market.

ZEBRA battery, so-called for the Zeolite Battery Research Africa Project.

Experimental Rechargeable Batteries

Experimental batteries live mostly in sheltered laboratories, communicating to the outside world through rosy reports generated for investors. Some systems show good potential, but many are years away from becoming commercially viable. Others disappear from the scene and die gracefully in the lab without hearing of their passing. Below are the most promising experimental batteries worth mentioning in alphabetical order.

Lithium-air (Li-air)
Li-air batteries borrow the idea from zinc-air and the fuel cell in that they breathe air. The battery uses a catalytic air cathode that supplies oxygen, an electrolyte and a lithium anode. Scientists anticipate an energy storage potential that is 5 to 10 times larger than that of Li-ion but speculate it will take one to two decades before the technology can be commercialized. Depending on materials used, Li-ion-air will produce voltages in between 1.7 and 3.2V/cell. IBM, Excellatron, Liox Power, LithionYardney, Poly Plus, Rayovac and others are developing the technology. The theoretical specific energy of lithium-air is 13kWh/kg; aluminum-air has similar qualities, with an 8kWh/kg theoretical specific energy.

Lithium-metal (Li-metal)
Most lithium-metal batteries are non-rechargeable. Moli Energy of Vancouver was first to mass-produce a rechargeable Li-metal battery for mobile phones, but occasional shorts from lithium dendrites caused thermal runaway conditions and the batteries were recalled in 1989. Li-metal has a very high specific energy. In 2010, a trial Li-metalpolymer with a capacity of 300Wh/kg was tested in an experimental electric vehicle (this compares to 80Wh/kg for the Nissan Leaf). DBM Energy, the German manufacturer of this battery, claims 2,500 cycles, short charge times and competitive pricing if the battery were mass-produced. Safety remains a major issue.

Lithium-sulfur (Li-S)
By virtue of the low atomic weight of lithium and the moderate weight of sulfur, lithium-sulfur batteries offer a very high specific energy of 550Wh/kg, about three times that of Li-ion, and a specific power potential of 2,500Wh/kg. During discharge, the lithium dissolves from the anode surface, and reverses itself when charging by plating itself back onto the anode. Li-S has good cold temperature discharge characteristics and can be recharged at 60C (76F). The challenges are limited cycle life of only 40 to 50 charges/discharges and poor stability at high temperature. Since 2007, Stanford engineers have been experimenting with nanowire and this technology offers promise. Li-S has a cell voltage of 2.10V and is environmentally friendly. Sulfur as the main ingredient is abundantly available.

Silicon-carbon Nanocomposite Anodes for Li-ion

Researchers have developed a new high-performance anode structure for lithium-ion batteries based on silicon-carbon nanocomposite materials. The material contains rigid and robust silicon spheres with irregular channels to promote the access of lithium ions into the particle mass. With graphite anodes, researchers have achieved stable performance and capacity gains of five times that of regular Li-ion. Manufacturing is said to be simple and low-cost, and the battery is safe and broadly applicable. However, the cycle life is limited due to structural problems when inserting and extracting lithium-ion at high volume.