Battery Materials

Literature Project

by
Fiona S. Oberbeck

Chemistry 713
Chemistry of Representative Elements
Dr. Hans-Conrad zur Loye
 Battery Materials
Fiona S. Oberbeck

Table of Contents

1. Introduction -2-
2. Conventional Batteries -3-
3. Future Battery Materials -4-
3.1 Ultra-fast Chargeable Batteries
-4-
3.2 Biological Components in Batteries -6-
3.3 Flexible Batteries -9-
4. Conclusions - 11 -
5. References - 12 -

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1) Introduction: [9,10,11]
Since the dawn of the computer age, everything has to be tiny, fast
and portable and the need for more improved battery materials is a big issue
for researchers. Making batteries which are light in weight, easy to recharge,
and especially non toxic if they ever get damaged is a goal that is not yet
manageable, but research has gone a long way in the last two centuries.
The first battery-like device was published by L. Galvani in 1791 who
did studies with froglegs6 finding that there is a current if the tissue of the
animal leg is connected to metal electrodes which was followed by A. Volta’s
experiments with electrochemical cells in 1800. Supposing that there are no
chemical reactions in a cell and that the cells are inexhaustible, Volta was
disproved by M. Faraday in 1834 who showed that the reactions in those
cells are not inexhaustible, but that there is an ion flow between the
electrodes. In 1836 J.F. Daniell managed to build the first battery with a
somewhat reliable current made of a zinc and a copper electrode with the
respective sulfate solutions, connected by a salt bridge to provide the ability
of ion flow. Because of this assembly’s simplicity it is still used in classrooms
to teach students the concept of batteries and the theories behind it. Twenty
three years later, in 1859, G. Planté invented the lead-acid battery which is
nowadays the oldest known rechargeable cell and the most commonly used
battery in cars. Using lead oxide and sulfuric acid,, it is also a quite
dangerous element whenit’s casing is compromised. In 1868 G. Lechlanché
invented the first single fluid electric generating battery which is still used
today in the zinc-carbon dry cell as a small rechargeable device. In the
following years the research for new battery materials had its renaissance
and is still a very important field since rechargeability, size of voltage output
and lifetime are still in development and have not yet been brought to
perfection. While the old devices with metal electrodes are still dominating
the market, researchers try to find various new ways to approach new
concepts for storing energy in ways that sick out compared to the last 150
years.

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2)Conventional Batteries
The most common and best known battery of today is the lead-acid battery
invented by Planté. It’s simple setup and its high voltage output makes it an
essential device for the auto industry since it can undergo about 500-800
recharges. Damaging on the mantle though can be dangerous for its user
since it holds diluted sulfuric acid which can cause serious irritation of the
skin and corrode random materials. Also the sulfuric acid can cause an
explosion of the battery if the engine gets too hot.
Another very common version is the alkaline battery which is commercially
available in various sizes and brands. The electrodes are made out of zinc
powder as the anode and manganese dioxide as the cathode with potassium
hydroxide serving as the electrolyte. With its nominal output of 1.5 V and the
ability to achieve higher voltage by adding several cells together, it is mostly
used for small electrical devices like digital cameras or portable video game
consoles. The alkali batteries are rechargeable, but over the time it is more
than likely that the potassium hydroxide will leak out and can cause skin
irritation.
The rival of the alkali batteries is the zinc-carbon dry cell which is also known
as a Leclanché cell. This cell consists of a zinc liner which serves as the
anode, a carbon rod in the middle surrounded by manganese (IV) oxide
which serves as the cathode, and ammonium chloride as the electrolyte. It is
a primary cell, meaning it is not rechargeable and has to be disposed after it
is discharged.
Equally popular but with a broader range of voltage, the lithium battery
reaches from an output of 1.5 V up to 3.7 V. Since there a many different
combinations of cathodes and electrolytes, the lithium battery can be used
with different cathodes but it always uses lithium as an anode. As well as the
cathode/electrolyte range, the toxicity of the components varies from setup
to setup. The downside of this cell is not just that it is mostly a primary cell
like the zinc-carbon dry cell, but also that it can discharge very rapidly when
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high currents are needed. One of the mostly used lithium cells is the lithium-
ion battery in which lithium is used as the anode, carbon as the cathode and
manganese or cobalt salts as the electrolytes. The lithium ions travel trough
the cell and are intercalated in the porous carbon. Unlike most lithium
batteries this process is reversible and the cell is therefore rechargeable. It
is, like the alkali battery, most commonly used in small electric devices.
Since all of the batteries listed above only have a very limited output and
lifetime, the need for long lasting, rechargeable, and powerful batteries with
outputs that can exceed the conventional devices nowadays the need for
new battery materials is given.

3) Future Battery Materials

3.1) Ultra-fast Chargeable Batteries5

A bright vision of the future are plug-in electric cars which do not
pollute the atmosphere, have a piped down engine noise and run at least the
same mileage per “tank” as conventional cars do. Sadly the reality is far
away from this vision. The first models of this kind are without a doubt more
silent than regular cars, but their efficiency is by far not comparable with a
gasoline powered car. The major problem though seems to be the charging
time of the batteries. Discharging times are too short and the time needed to
recharge the device is simply too long.
In studies done in the past this problem was faced in various ways. Since the
lithium battery seems to be the most promising application the studies were
focused on the different types of this battery and especially on the
procedures on the surfaces of the compounds. A recent project on this
research was done at the Massachusetts Institute of Technology using lithium
phosphate assemblies. Given that the main problem with lithium devices is
the migration through the electrolyte and the composites on the electrodes,
the goal is to improve the ion and electron transport along the surface and
through the bulk of the structure. One strategy to increase the rate
performance was to shorten the path length of the electrons as well as the
ions by introducing conducting nano-sized materials. During the studies it
was found that the lithium ions only move along the [010] direction into the
bulk and therefore attention was brought to increase the diffusion only in this
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direction since it is most efficient. Because it was found in previous studies

that doped lithium phosphates are very stable and efficient conductors,
LiFePO4 was used. To achieve the most effective compound, various
compositions of the LiFePO4 were synthesized and analyzed. Finally
LiFe0.9P0.95O4-δ was used for charge/discharge studies with very promising
results (figure 1).

Figure 15: a Discharge rate capability after a slow charge and hold at 4.3 V of different discharge times
(nC corresponds to a full discharge in 1/n hours); b Capacity retentions for full 50 full charge-discharge
cycles at constant 20C and 60C current rates. The voltage varied between 2.3-4.3 V

The electrodes for the charge/discharge studies are made out of 80 wt%
active material,
15 wt% carbon and 5 wt% polyethylenetatrafluoride as binder. In figure 1a,
between the longest and the shortest discharging time there are surprisingly
small differences in the capacity. For the 2C study the element still
discharged to its theoretically estimated capacity of about 166 mA h/g and
for the 50C study it only lost about 20% of its theoretical capacity. In figure
1b it is shown that even after 50 full charge/discharge cycles the capacity
retention is still given for the 20C
rate as well as for the 60C rate
which is very important for a
reliable device.
Further studies were made to
retrieve information about
electricity delivery at high rates
and therefore at very fast
discharging times. In figure 2
the discharge capability after
three different cycles for a discharge time of 18.3 seconds (197C) as well as
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Figure 25: Discharge capability at very high rates

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9 seconds (397C) are shown. Since the electrodes need to be able to keep up
with the high electron and ion migration, the composition of the electrodes
has been changed for the high rate studies into 30 wt% active material, 65
wt% carbon and 5 wt% binder. The capacity was lowered enormously but still
100mA h/g for the 197C rate and 60mA h/g for the 397C rate were achieved.
Considering that there is only the [010] travel direction makes the lithium
ions traveling with a speed of less than 1 ms per 50 nm, which is the
approximated particle size in the element. Since the limiting factor for
successful batteries is the delivery of the lithium ions and the electrons to
the surface and not just through the bulk, an amorphous layer with high
lithium ion mobility was added to take away the anisotropy of the surface
properties and therefore increase the ion delivery in the aspect of the [010]
traveling direction of the LiFePO4.
As a real application this battery might first be used in small devices
like MP3 players or cell phones where the charging time could be reduced to
10 s by using a 360 W source and a 360C rate for a 1 W h device. Taken to a
further level these results might allow electric cars holding a 15 kW h battery
to be charged within 5 minutes using a 180 kW source. It is shown that the
described batteries are able to deliver two orders of a magnitude more
energy than a conventional lithium-ion battery and the charging time is only
limited by the surface adsorption and surface transfer, which makes it able
to compete with supercapacitors.

3.2) Biological Components in Batteries2

A new and widespread method that can be found in nearly all fields of
research is the work with bacteriophages and viruses as templates for
nanostructures. Since tiny electric devices are more common than ever the
idea was near to use the well available natural templates also in the battery
research as a biological toolkit. Special bacteriophages are easy to modify
genetically by changing the sequence of the bases in the RNA or take out or
add whole sequence chains. Also the surface of the bacteriophages can be
easily modified by using the functional groups sticking out on the surface
since the structure of the common species is well known. Because the
biological templates have different structures on both endings the
bacteriophages can be assembled to long nanowires or in highly organized
structures. A.M. Belcher et al. at the Massachusetts Institute of Technology
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focused on using the M13 bacteria phage, which is 900 nm long and 6 nm in
diameter. In figure 3 a schematic image of the M13 bacteriophage and its
use in a high power device is shown. For better usage the major capsid gene
VIII protein was modified to make it usable as an a-FePO4 template and the
gene III protein was engineered to have high binding affinities for single-
walled carbon nanotubes (SCNs). Also a schematic diagram for the
fabrication of genetically engineered M13 is shown and its application in a
high-power lithium-ion battery cathode by powering a green light-emitting
diode.

Figure 32: a schematic image of a genetically engineered M13 bacteria phage; b schematic diagram of building a
high-power lithium-ion battery using the genetically engineered M13 bacteria phage as cathode with a photograph
of the device used to power a green LED

The modified M13 bacteriophage has tetraglutamate (EEEE) added to the N

terminus of each pVIII major coat protein subunit and is therefore called E4.
Since the presence of carboxylic acid groups is majorly increased, the E4 can
be used as a template for material growth hence the interaction with cations
is also increased. To increase the attachment to the SCNs the already
modified bacteriophage E4 had to undergo a second modification which does
not interfere with the original one. For this case the minor coat protein gene
III, which is located on the end of the bacteriophage, was chosen since the
insertion of a foreign DNA can be controlled independently from the pVIII
gene and the foreign DNA can encode the displayed peptides of the pIII
gene. In order to find the ideal DNA with a very high affinity to the SCNs a
variety of sequences were tried. The sequences N’-HGHPYQHLLRVL-C’,
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named MC#1, and N’-DMPRTTMSPPPR-C’, named MC#2, were chosen for

further experiments. It turned out that even that the histidine found in the
beginning of the sequence of MC#1, was observed often in bindings with
carbon nanotubes, the MC#2 clone had a binding affinity that was about four
times as high as the one from the MC#1 clone which again was about 2.5
times as high as the one found for the wild-type M13 bacteriophage. Even
with the SCN it was not possible to align the genetically engineered
bacteriophage, only the SCNs showed a highly organized structure (see
figure 4).

Figure 42: TEM images of multifunctional M13 bacteria phages. A EC#2 covered with a-FePO4 without
SCNs; B SCN only
without any interaction with the EC#2 a-FePO4; C-E SCN attached to EC#2 a- FePO4 on different magnifications

In order to show the electrochemical properties the E4 a-FePO4

bacteriophage was tested
without the SCNs first (see
figure 5). The measurements
were done at different discharge
rates hence the rates were kept
low. The rate performance in
figure 5D shows the Ragone
plot representing the specific
power versus the specific
energy.
It was found that all of the E4 a-
FePO4 nanowires hold anhydrous
Figure 5 : Characterization of the E4 a-FEPO4 nanowire
2

system; A TEM image of E4 a-FePO ; B TGA curve of E4 a-

4 silver attached to functional
FEPO4 nanowires; C and D electrochemical performance of E4
a-FEPO4 nanowires tested between 2.0 and 4.3 V groups on the bacteriophage.

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In further studies the SCN attached bacteriophages, holding 5 wt% of single-

walled carbon nanotubes, were tested for their electrochemical properties. To
see the actual difference cause by the special designed genetically
engineered bacteriophage various different clones were tested in figure 6A.
Furthermore a Ragone plot was used to show the improvement in the high-
power performance. Compared to figure 5D the improvement is clearly
visible for the SCN attached nanowire systems. In figure 6C the capacity
retention is shown which was taken for 50 cycles at a 1C rate.

Figure 62: Electrochemical properties of the a-FePO4 covered E4 clones of the M13 bacteria phage
attached to SCNs; A discharge curve at different rates for three different clones of the bacteria phage;
B Ragone plot for different modifications; C capacity retention for 50 cycles at a 1C rate

Overall it was found by comparing the two electrochemical studies that the
EC#2 modification with the SCN attachment is by far the better battery
material. The energy density of the EC#s clone was found to be three times
as big as the one for E4 for a specific power of 4 kW/kg at a rate of 10C. The
EC#2 clone showed a capacity of 134 mA h/g which shows the well improved
high-power performance. At a very low discharge rate of C/10 (10 hours) the
E4 clone showed a capacity of 143 mA h/g whereas the EC#2 clone
outplayed it by 27 mA h/g by showing a capacity of 170 mA h/g, which is an
incredible improvement.

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3.3) Flexible Batteries8

After tiny MP3 players flooded the market, the next possible new device
might be a music player embedded in cloth or in back packs. The major
problem is that all the batteries are stiff and cannot be bent at all. Flexible
devices would open this possibility for the market, but what does it take to
get a flexible battery?
Currently there are some studies about building batteries which are made
out of mostly plastic and avoid toxic and ignitable substances like acids or
heavy metals. Since those materials are primary elements, and therefore not
rechargeable, and have to be discarded after usage they are not very
efficient yet. To solve this problem miniature lithium-ion batteries have been
made with nanoparticles, like cobalt oxide covered virus templates as the
cathode and lithium foil as the anode. Because of the incredibly small
diameter of the metal oxide covering, the inorganic structure is very flexible.
It also has a very high rate of counter-ion and electron transport throughput.
Since inorganic structures sometimes can make it difficult for ions to move
because they bend them in intercalations and migrations there are still some
problems that are not completely solved yet.
As mentioned above, plastic elements were taken in consideration as well.
Because many problems can be controlled by changing different components
of the polymer, they have a big advantage over lithium-ion devices. Primarily
doped poly-acetylene compounds were used since their electric conductivity
is known since the 1970s. This research did not succeed though since the
poly-acetylene compounds have very low stability. As other polymers were
considered, polyaniline and polypyrrole were obvious choices since they
have reversible electrochemical doping behaviors. Unfortunately the doping
levels of these compounds were too low and also not very chemically stable,
which lead to self-discharge and therefore those materials were not efficient
enough for everyday use.
Other attempts were made to build a “sandwich” battery out of organic
materials (see figure 7) in which the R groups in the electrodes had different
redox potentials. The various R groups were attached to each other by
polymer chains which gave the device its flexibility and also made an
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electron hopping between neighboring R groups possible. During the

charging process the charge was stored by oxidation or respectively
reduction on the different R groups. The difference of the redox potentials
was the decisive factor for the voltage output.

Figure 78: Example of a flexible battery using an electrolyte captured between layers of polymers.

In spite of all those well elaborated features, the device still failed as well
since the redox reaction of the core-shell turned out to be electrochemically
irreversible and therefore it does not fulfill the requirements for a forward
looking battery.
Finally a successful application was found using organic polymers with
radicals like nitroxides. These devices have a completely reversible redox
reaction with fast electrode kinetics. Functioning as both electrodes (cathode
as well as anode), the radical polymers have a big advantage since they can
be easily tuned by changing the organic substituents in the two layers. These
radical polymer batteries are very flexible, semitransparent and can be
charged in less than 30 seconds. These new plastic batteries are compared
to the conventional lithium-ion batteries non toxic, safer, since they do not
hold an fluid electrolyte, and very easy to dispose. Also they are not limited
by natural resources since their main elements are carbon and hydrogen.

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4)Conclusions
Battery materials dominated a big research area over the last two decades
and yet it seems to the eye of a layman like there were no innovating
improvements. By taking a closer look, the research is rapidly progressing
and new ideas are realized every day. However the methods are not yet
improved enough to start large-scale productions.
In 3.1 it was shown that ultra fast chargeable and dischargeable batteries
are impending and that they are able to compete with the filling time of a
gas tank and might even be faster depending on the size of the
electrochemical element. Even though other metal compounds show equal
properties, lithium provides the biggest storage of energy with less weight
which could be important for the efficiency of an electric car. More optimized
electrode structures might push this device even further in its active energy
storing by improving the conductivity for high outputs over a very short
timeframe.
A research field that sounds at least as promising as the ultra fast charging
of lithium-ion batteries is the usage of biological components in energy
storage devices. The combination of the genetically engineered M13
bacteriophage together with the single-walled carbon nanotubes is not just
fast in charging and discharging but can also build miniature batteries which
are still surprisingly efficient with the good retention of the capacity for
various clones. By using different viruses or bacteriophages with equal
abilities for genetic modifications but smaller in size, the batteries might
even become more efficient since the area between the two electrodes
might be used even more efficiently. For further studies, it is necessary to
test shorter discharge time rates to get more information about useful

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changes on the electrodes or electrolytes of the battery. The simplicity,

affordability, and availability of the particles make this field very promising
for the future.
The flexible devices described in 3.3 also give a broad outlook for the future
since they open a whole field for energy storing with the organic radical
polymers. Given a broader variety of R groups, the devices might be able to
become even more efficient. Because there are no metals used they are
more environmentally friendly in case of damage on the electrochemical
element.
Because of the wide variety of battery materials, only three different fields
were mentioned in this paper. Yet there is still a large number of other
promising fields like completely biological devices or an inexhaustible
number of solid state elements which were not discussed. Overall the
research on new battery materials is not yet exhausted but gives hope of a
soon coming innovation on the large-scale market.

5) References:

1) M. Armand, J.-M. Tarascon; Building better batteries; Nature, 451

(2008), 652-657

2) Y. J. Lee, H. Yi, W.-J. Kim, K. Kang, D. S. Yun, M. S. Strano, G. Ceder, A.

M. Belcher; Fabricating Genetically Engineered High-Power Lithium-Ion
Batteries Using Multiple Virus Genes; Science, 324 (2009), 1051-1055

3) J. Alper; The Battery: Not Yet a Terminal Case; Science, 296 (2002),
1224-1226

4) B.C. Sales; Smaller Is Cooler; Science, 295 (2002), 1248-1249

5) B. Kang, G. Ceder; Battery materials for ultrafast charging and

discharging; Nature, 458 (2009), 190-193

6) N. Kipnis, Luigi Galvani and the Debate on Animal Electricity, 1791-

1800; Annals of Science, 44 (1987); 107-142

7) http://www.nature.com/news/2008/080818/full/news.2008.1047.html

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8) H. Nishide, K. Oyaizu; Toward Flexible Batteries; Science, 319 (2008),

737-738

9) E. Riedel, “Anorganische Chemie” 6th Edition, Walter de Gruyter, Berlin

2004

10)http://acswebcontent.acs.org/landmarks/drycell/history.html

11)http://www.ideafinder.com/history/inventions/battery.htm

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