LNEG - National Laboratory for Energy and Geology

Introduction

Hydrogen Production
Technologies
Focussing LT
Water Electrolysis
HYDROGEN PRODUCTION
TECHNOLOGIES
C. M Rangel, A.Gano, A.I. de Sá, P.Pinto
carmen.rangel@lneg.pt

Key Performance Indicators

Hydrogen in the energy transition

Flexibility of the system through storage capability

Produced by primary sources regionally prevalent

Critical in the increase of renewables in the energy mix

 Hydrogen in unprecedented momentum

Source: Hydrogen Council, 2020

PNEC aligned with the main instruments of public policies

Route towards
Carbon Neutrality in 2050

Strategic Investment in Energy

and Climate

Opportunity for Hydrogen in the present decade in the

framework of Investments based on the definition of a National
Strategy for Hydrogen
Research and Innovation
and support to large scale demonstration initiatives to which the
Hydrogen RoadMap was instrumental.
Decarbonization of the Economy
Value chain
 Export
Grid Storage

Electrolysis

Solar Heating
Industry
Wind

Transport

Reforming
CCS

Fertilizer
Production
EN-H2 Estratégia Nacional para o Hidrogénio
Green Hydrogen production cost projected 2019, Hydrogen Council 2020
H2 Technologies Worldwide
Transportation
Hydrogen and Fuel Cells

SOLAR
Photocatalysis
Thermochemical
WATER
Low and High Temperature
Electrolysis
BIO & WASTE

Biomass Gasification

FOSSIL
Hydrogen Production worldwide
Production capacity by country-
Europe
País Hidrogénio (109 m3) País Hidrogénio (109 m3)

Alemanha 21.5 Bulgária 1.8

Holanda 10.1 Suécia 1.3

Reino Unido 7.6 Portugal 1.2

França 7.1 Hungria 1.0

Itália 6.6 Eslováquia 0.9

Espanha 5.9 República Checa 0.9

Bélgica 5.7 Irlanda 0.9

Roménia 5.5 Grécia 0.8

Polónia 4.2 Croácia 0.8

Áustria 1.9 Eslováquia 0.6

Finlândia 1.8 Dinamarca 0.2

Total ----- ------ 88.3

 Hydrogen in Portugal
Capacidade Processo /
Região Concelho Companhia Utilização Disponibilidade
(103 m3/dia) matéria prima

Baixo
Estarreja Uniteca 9 n.e. n.e. Subproduto
Vouga

Baixo Reforma a vapor

Estarreja Air Liquide 76 n.e. Venda
Vouga do metano

Fornecimento
Baixo Reforma a vapor
Estarreja Air Liquide 120 Quimigal para Venda
Vouga do metano
produção de anilina
Eletrólise de
Baixo
Estarreja Uniteca 50 soluções de n.e. Subproduto
Vouga
cloreto de sódio
GDP
Grande
Lisboa (Gas de n.e. n.e. n.e. Venda
Lisboa
Portugal)
Eletrólise de ácido clorídrico e
Gande Póvoa
Solvay 39 soluções de peróxido de Subproduto
Lisboa Santa Iria
cloreto de sódio hidrogénio

Grande Póvoa
Solvay 28 Clorato de Sódio n.e. Subproduto
Lisboa Santa Iria

Alentejo
Sines Repsol 187 Etileno n.e. Subproduto
litoral
Reforma a vapor
Alentejo
Sines Galp 1 550 de nafta ou refinaria Cativo
litoral
metano
 PRODUCTION
TECHNOLOGIES
 H2 Production
Photocatalysis_Increase of yield of the reaction. Develop more efficient and durable
catalyst for visivel light use. Development of
photoreactors to enter large scale prototypes and industrial use.
PEM_Reduce cost to 800 USD/kW. Optimization of membranes.
Reduction of the amount of noble metals Increase efficiency to 80%
SOLAR
HHV.Increase lifetime to 50 000 h. Increase capacity of stack to
multiple MW. Attain start-up periods compatible with those existing Photocatalysis
energy markets
Thermochemical
Alkaline: Reduce cost to values lower than 900 USD/kW.
Increase efficiency to 75% HHV.) Increase current
WATER
density through increase in pressure and temperature of
operation. Increase pressure of operation and minimize Low and High Temperature
need to pressurize hydrogen.
Electrolysis

BIO & WASTE Reduction cost of reactors and process of gas

separation. Increase catalyst efficiency.
Biomass Gasification Reduction cost in the preparation and handling of
the biomass, in CCS and optimization of the energy
FOSSIL balance of the process. Quality control of hydrogen.

Methane Steam Reforming As environmental constraints and CO2 price increase, efficient CO2
capture technologies will have to be put in place.

Additional H2 purification systems will have to be developed in

order to achieve fuel cell requirements.
 WE and SMR

Scenario WE dominant
WE Drop cost of electrolysis and renewable
electricity

SMR/ATR

By-product

WE

Scenario SMR/ATR dominant

CCS feasible and politically accepted.

 The “colours” of Hydrogen

includes a threshold on the GHG emissions (based on an LCA approach) of the produced hydrogen. To be called “green hydrogen”, carbon
footprint below 36.4 g CO2equ/MJLHV. The percentage of green hydrogen of a production is equivalent to the percentage of renewable
sources (energy including ancillary energy requirement and feedstocks) used for the production.
“blue hydrogen” if the carbon footprint is lower than 36.4 g CO2/MJ. In order to restrained the carbon emissions to the proposed levels the
capture and storage or re-used of CO2 is envisaged. This adds to the cost of “blue hydrogen”.
“ Grey Hydrogen” is hydrogen produced with emissions higher than 36.4 g CO2/MJ, be it from renewable or non-renewable sources. At the
moment, grey hydrogen is cheaper than either blue or green hydrogen but it carries an added cost in terms of the price of CO2 emissions.
The scope of the markets has prompted the need for certificates that label the origin and quality of the product and the hydrogen
production pathway.
 WATER
ELECTROLYSIS
 Electrolysis of Water
Cell Potential and Thermodynamic Feasibility

Half reactions in the electrolysis of pure water at pH=7, and at 25°C

At cathode: 2H2O(l) + 2e– → H2(g) + 2OH– E° = -0.42 V

At anode: 2H2O → O2(g) + 4H+ + 4e– E° = +0.82 V

The net reaction of electrolysis of water

2H2O(l) → 2H2(g) + O2(g) E° = -1.24 V

The cell potential of electrolysis of pure water is negative and hence is

thermodynamically unfavourable.

Low concentration of ions and the interfaces to be crossed

extra voltage (Overvoltage) at each electrode is needed
 Electrolysis of Water
Water Electrolysis in the Presence of Acids
Additional hydrogen ions from acid will be reduced at the cathode while water will be
oxidized at the anode.

At cathode: 2H+ + e– → H2 E° = +0.0 V

At anode: 2H2O → O2(g) + 4H+ + 4e– E° = +1.23 V
Net reaction 2H2O → O2(g) + 2H2 E° = -1.23 V
T

Water Electrolysis in the Presence of Bases

Additional hydroxyl ions, release their electrons to anode, while electrons at cathode
oxidize water molecules near it. Half reactions of electrolysis in the presence of a base

At cathode: 2H2O(l) + 2e– → H2(g) + 2OH– E° = -0.83 V

At anode: 4OH– → O2 + 2H2O + 4e– E° = +0.4 V
Net reaction 2H2O → O2(g) + 2H2 E° = -1.23 V
.
Water Electrolysis in the
Presence of Salts
Salts dissociate into cations and anions in water, increase the ionic
concentration for increasing conductivity.

Cations and anions could become competitors to the decomposition of

water to produce hydrogen and oxygen.

The selection of salts with non-competing ions becomes necessary.

Salts containing lesser standard electrode potentials than hydrogen and

hydroxide ions are suitable for the electrolysis of water.
Ions of first and second group elements (Li, Na, K, Mg, Ca, Ba, etc.) have
lower standard potential than hydrogen ions and will not be reduced and
allow hydrogen ions from water to hydrogen.
.
.

Electrolyzers
The electrolytic cell used for the electrolysis of water is the electrolyzer.
Depending on the transporter of the electrolyte, electrolyzer can be divided
into three types;

Polymer Electrolyte Membrane (PEM) Electrolyzer

A polymer such as Nafion separates the electrodes and allows hydrogen
ions formed by the oxidation of water at the anode to pass through it to the
cathode compartment for discharge and form hydrogen gas.

Alkaline Electrolyzers
Aqueous sodium (or potassium) hydroxide used in the electrolysis provides
and movement of hydroxide ions to the anode to form oxygen.

Solid Oxide Electrolyzer

Ceramic oxide separates the electrodes. At the cathode, water is reduced to
hydrogen and oxide ions. The oxide ions pass through the ceramic oxide to
the anode to become oxygen gas. This is used at high temperatures of 700
to 800°C to reduce the external voltage needed for electrolysis.
PEM Electrolyser System Design
PEM electrolyser
Electrolysis of Water_E vs i
EFFECTS of TEMPERATURE and PRESSURE
Electrolyzer Cell Components
 Water electrolysis installed capacity

In [ Z. Chehade et al, 2019][1] :

Green hydrogen is currently

enjoying unprecedented political
and business momentum, with
the number of policies and
projects around the world
expanding rapidly.

In 2018, over 20 MW of
electrolyser capacity has been
commissioned and, since then,
projects of up to 20 MW( Delfzilf,
The Netherlands) and 100 MW Cumulative capacity of the Alkaline and PEM
technologies
have been announced (Port of
Hamburg, Germany). [1] Z. Chehade, C. Mansilla, P. Lucchese, S. Hilliard, and J. Proost, “Review
and analysis of demonstration projects on power-to-X pathways in the
world,” International Journal of Hydrogen Energy, vol. 44, no. 51, pp.
27637–27655, Oct. 2019, http://dx.doi.org/10.1016/j.ijhydene.2019.08.260
Custos do Hidrogénio/ tecnologias

Fontes: Direção-Geral de Energia e Geologia [9]

Custos (LCOH) atuais e futuros das cadeias de valor do hidrogénio dirigidas para a mobilidade.
São consideradas estações de abastecimento de média dimensão (< 1500 kg H2/dia)
 KEY
PERFORMANCE
INDICATORS
Main characteristics of PEM and Alkaline electrolysers

For the analysis of the most relevant key

performance indicators the electrolyser system is
considered to include
the power supply unit with the system control
subsystem, the process utilities, the process
cooling and the gas cooling and drying unit.

The external compression, external purification

and hydrogen storage units are generally excluded
from the key parameters definitions.

KPI´s
electrical energy consumption and efficiency,
operational conditions, flexibility and reactivity to
changes in input conditions and loading effects,
durability and lifetime, safety and capital
investment (CAPEX) and operational (OPEX) costs
 Electrical energy consumption and efficiency
Electrical Energy
Consumption
Reference Timeline
Main aspects [kWhel/kgH2]
Alkaline PEM
2020 49-67 44-61
[FCH-E4Tech Report, 2014]
2030 48-63 44-53
• Different system designs and 2020 53-60 52-62
operating strategies [O. Schmidt et al, 2017]
2030 53-60 49-58
• Depends on operating points [FCH, State-of-the-Art and 2020 50 55
and power requirements Future Targets (KPIS),
2030 48 50
2018]
• electrolyser ‘efficiency’ is considered 2020 50-60 50-65
as the energy input in kWh per kg of 2030 45-60 45-60
hydrogen output. For commercial
Reference values for 10 MW systems
technologies (alkaline, PEM) this • Presently both technologies are comparable in
energy is supplied in electrical form, 49 to 55 kWh /kg
Key facts
el H2 terms of energy requirements with a some
with a theoretical minimum for alkaline electrolysersadvantage for Alkaline technologies.
electrical energy input of 39.4 and
kWh/kgH2 (HHV of hydrogen). • In a medium term trend (2030), PEM
52 to 55 kWhel /kgH2 electrolysers should increase efficiency and
for PEM electrolysers require less energy consumption, making both
technologies slightly equivalent in terms of
energy consumption per kg of Hydrogen
produced.
 Durability and lifetime
Stack Lifetime [Hours]
Reference Timeline
Alkaline PEM
Main aspects 2020
90 000 - 100 50 000 - 90
000 000
[FCH-E4Tech Report, 2014]
90 000 - 100 60 000 - 90
2030
000 000
• Degradation is typically given as a 40 000 - 80 20 000 - 90
2020
voltage increase (μV/hour), and is [O. Schmidt et al, 2017]
000 000
40 000 - 80 40 000 - 10
often not included in technical 2030
000 000
data sheets of commercial 60 000 - 90 30 000 - 90
2020
products. [IEA Report, 2019]
000 000
90 000 - 100 60 000 - 90
2030
000 000
• A linear voltage degradation of [FCH, State-of-the-Art and Future 2020
1μV/hr translates into an Targets (KPIS)] 2030
additional electrical energy input 2020
50 000 - 90 30 000 - 90
of ~2 kWh/kgH2 after 60,000Reference
hours values: 000 000
Alkaline electrolysers 80 000 - 90 60 000 - 90
of continuous operation. voltage degradation less than 1 -2 µV/hour
2030
000 000
PEM electrolysers
• Presently Alkaline stacks show a greater
• Literature data and data received
from manufacturers suggest Key
voltage degradation less than 4 - 8 µV/hour
expected lifetime than PEM stacks
• In a medium term (2030), with an increasing
degradation under continuous
operation covers a wide range of facts maturity of PEM technologies and processes,
state-of the-art PEM electrolysers will tend to
0.4–15μV/hr. achieve the same performance.
 Operation Dynamics and Flexibility

In the 2014 FCH Report [1] and in [O. Schmidt et al, 2017][2] In the 2014 FCH Report [1]
Minimum part load operation 2020 2030 Ramp up from minimum part load
2020 2030
point to full load
Central Value 15% 15%
Alkaline Central Value 17% 17%
Range 10% - 20% 10% - 20% Alkaline
Range (1) 0.13% - 25% 0.13% - 25%
%(full load) %(full
Central Value 4% 4% load)/second
Central Value 40% 40%
PEM PEM
Range 0% - 5% 0% - 5% Range (2) 10% - 100% 10% - 100%
(1) Based on data from three alkaline manufacturers
(2) Based on data from three PEM manufacturers
In the 2014 FCH Report [1] :
Ramp down from full load point to
Startup time - from cold(1) to 2020 2030
2020 2030 minimum part load
minimum part load
Central Value 25% 25%
Central Value 20 20 Alkaline
Alkaline (2) Range (1) 25% - 25% 25% - 25%
20min – 20min – %(full
Range /second
minutes several hours several hours load)
Central Value 40% 40%
PEM
Central Value 5 5 Range (2) 10% - 100% 10% - 100%
PEM (3)
Range 5 - 15 5 - 15
(1) Based on data from three alkaline manufacturers
(2) Based on data from three PEM manufacturers
 Operation Dynamics and Flexibility
Main aspects
• The minimal part load limitation
of electrolysers is given by the
cross-diffusion of product gases
through the membrane, which is
particularly severe at low loads
and can result in flammable gas
mixtures. This phenomenon is
more important in alkaline
electrolysis than PEM electrolysis.
• PEM electrolysers have shorter
cold start-up times and faster
ramp rates compared to alkaline
electrolysis following from the
more compact design and lack of
liquid electrolyte.
Key facts
In general, PEM electrolysis
offers more flexibility compared
to Alkaline, in terms of minimum
part load operation and
response times.
Associated safety issues
• Hydrogen diffusion across the membrane to the oxygen
side is a critical safety issue mainly in alkaline electrolysis.
• Pressure and temperature variations due to intermittent
operation will induce high mechanical stresses to the
stacks, to the balance of plant, especially to components
ensuring tightness of the system, and might increase the
risk of gas or liquid leaks.
 Investment Capital Costs (CAPEX)
In the 2014 FCH Report [1]

In [O. Schmidt et al, 2017][2]

System cost (*) 2020 2030
System cost (*) 2020 2030
Central Value 630 580 (400)
Central Value 800 650 (400)
Alkaline
Range 370 - 900 370 - 800 Alkaline
EUR/k Range 700 - 1000 700 - 1000
EUR/k
W Central Value 1000 760 (500)
W Central Value 1300 1000 (500)
PEM
Range 700 - 1300 250 - 1,270 PEM
Range 800 - 2100 700 - 1800

(*) Incl. power supply, system control, gas drying (purity above 99.4%).
Excl. grid connection, external compression, external purification and
hydrogen storage
[1] FCH 2 JU, E4Tech, “Study on development of water electrolysis
in the EU – Final Report”, 2014. Available:
https://www.fch.europa.eu/sites/default/files/study%20electrolyse
r_0-Logos_0_0.pdf
(*) Average values from Industry experts only.
[2] O. Schmidt, A. Gambhir, I. Staffell, A. Hawkes, J. Nelson, and S. Few,
“Future cost and performance of water electrolysis: An expert elicitation
study”, Int. J. Hydrogen Energy, vol. 42, no. 52, pp. 30470–30492, Dec.
2017, http://dx.doi.org/10.1016/j.ijhydene.2017.10.045
 Investment Capital Costs (CAPEX)

In [2019 IEA Report][2]

Capital cost investments

in PEM systems will
decrease faster than in
Alkaline when
considering large scale
multi-stack electrolyser
systems

[2] IEA, “The Future of Hydrogen - Seizing today’s opportunities” IEA, no. June, 2019.
Available: https://www.iea.org/reports/the-future-of-hydrogen
COST/SIZE
Cost breakdown
Partição de custos para um electrolisador PEM de 1 MW
(Sistema, BOP e Stack)

Stack_ 50% do custo do sistema sendo dominado pelas placas bipolares

redução de custos pela alternativa de materiais avançados com melhor desempenho e
durabilidade.

Electrolisador BOP
45%
PEM Componentes Stack
55%
Custos

Electricidade
8%
Camadas porosas
Circulação
BOP Água
22%
Selagem 17% Processamento
24% 50%
H2
3%
Placas bipolares STACK Arrefecimento
3%

Assembly e placas As CCM (catalyst coated membranes) custo

estruturais
53% (tipicamente 10% do custo do stack),
CCM membrane integram materiais críticos que podem
representar limitações ao scale-up.
Electrolyser Cell Materials
PEM

V= 1.6 V
i= 1.8 Acm-2
P=2.9 W cm-2
Anode Pt-Ir 7 gm-2
Cathode Pt 4 gm-2
Investment Capital Costs (CAPEX)
System cost [EUR/kW]
Reference Timeline
Alkaline PEM
2020 370 - 900 700 - 1300
[FCH-E4Tech Report, 2014]
2030 370 - 800 250 - 1270
2020 700 - 1000 800 - 2100
[O. Schmidt et al, 2017]
2030 700 - 1000 700 - 1800
2020 400 - 900 700 - 1300
[A. Buttler, H. Spliethoff, 2018]
2030 400 - 800 300 - 1200
2020 600 - 1400 1200 - 1800
[Proost, 2019]
2030 700 - 900 200 - 800
2020 450 - 1250 1000 - 1600
[IEA Report, 2019]
2030 350 - 750 600 - 1350
[FCH – State-of-the-Art and Future 2020 600 900
Targets (KPIS), 2018] 2030 400 500
2020
2030

Key facts • Presently the capital investment in Alkaline based

electrolysers is inferior to those with PEM stacks

• Existing CAPEX analysis show a clear trend of

decreasing costs of PEM based electrolysers in a
medium term basis, namely when considering large
scale multi-stack electrolyser systems, making both
technologies almost cost equivalent.
Weight of electricity(%) in the GHG emissions per kg of hydrogen along life cycle for alkaline electrolysis
(efficiency 68%, mix PT 2030)

Source: DGEG Integração do Hidrogénio nas Cadeias de Valor, 2019

Renewable hydrogen from electrolysis production cost scenarios,
USD/kg hydrogen
Source: Hydrogen Council, “Path to hydrogen competitiveness
- A cost perspective”, 2020
https://hydrogencouncil.com/wp-content/uploads/2020/01/Path-to-Hydrogen-Competitiveness_Full-
Study-1.pdf

An electrolyser CAPEX of
500$/kW – access to
renewables at 20$/MWh
enables production of
renewable hydrogen at about
2$/kg.

Source: Hydrogen Council, 2020.

 Operational Capital Costs (OPEX)

In the 2014 FCH Report [1]

OPEX
Plant Size [% of initial capex per
[MW] year]
1 5%
Operational costs (*) 2020 2030
5 2.20%
10 2.20%
Alkaline Range System 15-53 6-47
20 1.85%
EUR/kW/year size
50 1.64% PEM Range dependent 28-70 4-54
100 1.61%

(*) Excluding electricity costs

Estimated - this excludes the cost of stack replacements at the scheduled end
operational cost as a of a stack lifetime
percentage of initial
capex for different
plant sizes
[1] FCH 2 JU, E4Tech, “Study on development of water electrolysis
in the EU – Final Report”, 2014. Available:
https://www.fch.europa.eu/sites/default/files/study%20electrolyse
r_0-Logos_0_0.pdf
 Operational Capital Costs (OPEX)

Main aspects
Operational costs (opex) exclusive of electricity and
stack replacement found in literature are typically 3-4%
Key facts
of the initial capital expenditure (capex) per year, with
little difference among different chemistries. • OPEX costs, in terms
Manufacturers emphasize the fact that this number is of percentage of
very sensitive to location (labour cost) and size. initial CAPEX, is very
dependent on the
Used an approach that relates consumables, i.e.
material cost for planned and unplanned maintenance,
power plant
to the capex (1.5% of initial capex per year)6. specification

On top of the consumables, estimated labour cost in • PEM technology

central Europe are added for regular checks by the
operator as well as planned and unplanned shows lower OPEX
maintenance works, which all depend on system scale. cost ranges, trending
to decrease till 2030
Alkaline vs PEM
KEY Performance indicators
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