PEM water

electrolysis
fundamentals
Dimitrios Tsiplakides

Hydrogen production
Production and consumption of hydrogen
Only 0.25% of
hydrogen produced
worldwide was
produced by
electrolysis

HYDROGEN
Encyclopedia of Electrochemistry, Volume 5: Electrochemical Engineering, Wiley (2007)

Electrolytic process is
only competitive when
the cost of the
electricity is low

The electrolysis of
water has received
considerable attention
in the context of the socalled hydrogen
economy

Hydrogen production

Hydrogen is fastest growing industrial gas

Central
production

Distributed
production

Commercial plants using

alkaline electrolysis have
operated at capacities
over 60,000 kg /day for
industrial chemical
processing

Produced at station to
enable low-cost delivery

Renewable plants using

renewable feedstocks
(wind, solar, etc.) are
envisioned in longer term

Currently available using

grid electricity

2015 Targets*
cost of hydrogen delivered at a refuelling station of less than 5 /kg (0.15 /kWh)

Renewable
demonstration systems
using PEM electrolysis
already in place at select
locations

capital cost of 1,500-2,500 /kW for industrial units and 4,000-5,000 /kW for micro-CHP
*

(FCH-JU)

What is water electrolysis?

Electrolysis of water is the decomposition of

water (H2O) into oxygen (O2) and hydrogen
gas (H2) due to an electric current being
passed through the water.

H2O H2 + 1/2O2

Thermodynamics
H2O H2 1 / 2O2 Hor 286kJ / mol*
(endothermic: energy has to be applied)
Ideal gas enthalpy of
formation, kJ/mol
0
0
-286.03

O2
H2
H2O (liquid)

Ideal gas entropy,

kJ/molK
0.205
0.130
0.069

Perry's Chemical Engineers' Handbook, Section 2.Physical and Chemical Data

So SoH 1 / 2SOo SoH O 0.163kJ / mol K

2

Ho HoH 1 / 2HOo HHo O 286.03kJ / mol

2

Go Hor So (286.03 0.163 T) kJ / mol

Go corresponds to the
minimum share of Ho
which has to be applied
as work, e.g. electricity

TSo corresponds to the

maximum share of Ho which
can be applied as thermal
energy to the process.

water is liquid

Thermodynamics

The minimum necessary cell voltage to start water electrolysis is the reversible
(no losses in the process) potential:
Go

Vrev

n F

n=number of electrons transferred (n=2)

F=Faradays constant (F=96487 C/mol)

Example: at 25oC Vrev=1.23 V

Precondition: heat corresponding to TS CAN be integrated into the process

The potential at which the cell operates adiabatically (heat is not lost or required)
is the thermoneutral potential:
Ho

Vth

n F

Example: at 25oC Vth=1.48 V

Vth accounts for the missing energy when thermal energy cannot be added from the surroundings (low
temperature process)

Thermodynamics

The importance of thermoneutral potential for water electrolysis

The cell is heated by the excess

energy generated by the joule
heat caused by the overpotentials
Vth (1.48V)
The cell will cool as the cell
dissipates the heat associated
with the entropy change,
irreversibly
Vrev (1.23V)

cell potential

Vth is higher than Vrev as it

contains the heat
associated with the
entropy change for the
reaction.

Thermodynamics

Thermodynamics

The electrolysis efficiency is defined as the thermoneutral potential over the

operating voltage (the higher heating value (HHV) of one mole of the product
divided by the energy consumption):

Ho Vth

G
V

Isothermal operation, i.e. by applying the thermoneutral potential, corresponds to 100%

efficiency in electricity-to-chemical energy conversion.

Theoretical efficiencies greater than 100% are possible when the cell operates at a lower
potential than the thermoneutral potential (and greater than reversible potential, Vrev). In
this case, external heat is required to supply the remaining energy required (-S).
Example: electrolysis at 25oC: max = (1.47V / 1.23V) = 120% !

The operational potential is defined by the optimization of production economy. The

higher the cell voltage is increased above Vrev the higher is the current density and in
turn the production rate.

Thermodynamics

Effect of temperature
At elevated temperatures a significant part
of the total energy demand can be
provided as heat
This provides an opportunity to utilize the
Joule heat that is inevitably produced due
to the passage of electrical current
through the cell
In this way, the overall electricity
consumption and, thereby, the H2
production price can be reduced

Thermodynamics

Effect of pressure

pH O
RT
2
ln
The equilibrium potential, E, is described by the Nernst equation: V V
nF pH p1O/2

Eo Nernst potential at standard pressure (=Go/nF)

If we assume that the overall pressure is equal at both electrodes, the increase of E with
pressure is given by:
RT
1
V (V V ) ln 1/2
nF p

Example: an increase in the overall pressure from 1 atm to 200 atm corresponds
to an increase in E by only 34mV (@ 25oC) and 48mV (@150oC)!
Pressurization is advantageous due to:
a) Reduction of internal cell resistance
b) Production of compressed hydrogen facilitates storage
c) Reduction of volume of gas bubbles facilitates water transport

Thermodynamics

Current density-voltage diagrams

In a working electrolysis cell, irreversibility of
various processes is unavoidable, which leads
to a cell voltage V > Vrev:

V Vrev | cat | an i R A conc

cat
an
iRA
RA
an

overpotential at the cathode

overpotential at the anode
ohmic losses within the cell and its components
area-specific ohmic resistance
concentration overpotential (mass transport limitations)

Due to the more complex oxidation at the

anode (the OER contains an overall transfer of
4 electrons), the overpotential at this electrode
is dominant (cat > an).

Types of electrolyzers
Alkaline

Acid

Polymer
electrolyte

Solid oxide

OH-

H+

H+

O2-

water

water

water

water, CO2

Electrolyte

Sodium or
Potassium
hydroxide

Sulphuric or
Phosphoric
acid

polymer

ceramic

Electrode

Raney Ni

Pt

Pt, Ir

Ni-cermet

Temperature

40-90oC

150oC

20-150oC

700-1000oC

Type
Charge carrier
Reactant

Types of electrolyzers

Overall reaction: H2O H2 + 1/2O2

Half-cell reactions
Type

Charge carrier

Alkaline

Acid

Polymer
electrolyte

Solid oxide

OH-

H+

H+

O2-

2H 2e H2

2H 2e H2

H2O 2e H2 +O2

H2O 1 / 2O2

Cathode reaction
(HER)

2H2O 2e

Anode reaction
(OER)

2OH H2O

H2O 1 / 2O2

1 / 2O2 2e

H2 2e

H2 2OH

H2 2e

O2 1 / 2O2 2e

Classical water electrolysis

Alkaline electrolysis

Alkaline electrolyte electrolyzers represent a very mature technology that is the current
standard for large-scale electrolysis.

Common electrolyte: aqueous potassium

hydroxide (KOH) at 30% concentration
Operation Conditions: 70-100oC and 1-30bar
Operational voltage: 1.7-2.2 V (@ 0.2-0.6 Acm-2)
Can utilize cost effective electrode materials
(iron, nickel, nickel compounds)
Diaphragm often asbestos
Efficiency: 70-80% (based on hydrogen HHV)
2OH H2O 1 / 2O2 2e

2H2O 2e H2 2OH

Classical water electrolysis

Alkaline electrolysis

Advantages

Low specific
production rate
Low efficiency
Large system
size

Drawbacks

Require cheap
electrodes
Cheap
construction
material

PEM electrolysis

Operational principle
PEM electrolysis is a process just reverse of
a PEM fuel cell process; however the
materials are typically different from PEM-FC
The heart of a PEM or SPE electrolyser is a
proton exchange membrane (or solid
polymer) electrolyte

H2O 1 / 2O2 H2 2e

2H 2e H2

H2O H2 + 1/2O2

PEM electrolysis

Historical facts

The first solid polymer electrolysers (SPE)

were developed by the General Electric
Company as fuel cells for the NASA space
programme (project Gemini).

Subsequently, small-scale SPE water

electrolysers were used for military and space
applications in the early 1970s (active cathode
areas per cell: 0.02 m2)

In 1975, a development programme was

established to scale-up the technology
targeted towards large-scale, commercial
applications such as energy storage (active
area: 0.093 m2 and then 0.23m2 per cell
involving a 200 kW module capable of
producing 55 m3h-1 H2)

PEM electrolysis

Performance optimization
Components resistivity
Membrane thickness, ion-exchange capacity
Oxygen kinetics

Ecell ln

R R
*

dif

i
i R
io

R bipolar R electrolyte R contact

Current efficiency (or Faradaic efficiency):

molar H2 rate production divided by (i/2F)

PEM electrolysis

Components

Membrane Electrode Assembly (MEA)

Schematic of PEM electrolyser

showing the location of the components

Membrane
Anode and Cathode electrode

Gas diffusion Layer (Current collector)

Bipolar plates

Components cost

PEM electrolysis

Proton exchange membrane

Requirements

high protonic conductivity for the transport of ions

high oxidative stability
sufficient mechanical and thermal stability
low permeability for gases to prevent mixing of the gases
produced
electric insulator to prevent short-circuits within the cell for
electrode to electrode
Ionomer must have high chemical and mechanical stability
to withstand the harsh conditions in a PEM electrolysis cell

Proton exchange membrane

Supported Membranes (Dimensionally Stable Membranes, DSMTM)

Perfluorosulfonic acid (PFSA) ionomer incorporated in an engineering

plastic support (Nafion, Fumapem, Flemion, Aciplex )
High strength
High-effisciency
No x-y dimensional changes upon wet/dry or freeze-thaw cycling

PFSA

PEM electrolysis

Alternative Membranes

Bi-Phenyl Sulfone Membrane (BPSH)

Hydrocarbon/Phosphonate Membrane
Inexpensive starting materials
Trade-off between conductivity and mechanical properties

PFSA (700 EW & 850 EW) membranes

Optimization of ionomer EW and thickness, scale-up fabrication methods
and techniques, and improve costs

PA doped poly [m-phenylene-bis(5,50-benzimidazole)] (PBI)

Aromatic polyethers containing pyridine groups (H3PO4 doped)

BPSH
N

z
N

ADVENT TPS

PEM electrolysis

Proton exchange membrane: Performance

PEM electrolysis

Proton exchange membrane: Durability

Indication of
membrane
degradation

Membrane degradation
F- release rate: 3.7 g/hr (<10 ppb)
Estimate lifetime: ~55,000 hrs

PEM electrolysis
Catalysts
Mixture of catalyst and ionomer in order to enlarge the area of threephase-boundary where half-cell reactions take place.

Hydrogen side: Supported or unsupported Platinum (loading:

1-6 mgcm-2).

Oxygen side: Unsupported iridium, ruthenium and their oxides

and mixtures (loading: 1-2 mgcm-2):
Ruthenium oxide (RuO2) is the most active material for OHR; yet it is highly
unstable (the oxidation of RuO2 to RuO4 occurs at potentials more positive
than 1.387V)
Iridium oxide (IrO2) is the standard material compromising activity and
stability. Used pure or mixed with other precious (e.g. Pt) or non-precious
metals.
Binary and ternary unsupported catalysts (SnO2, TaO2, SbO2, TiO2, Ti4O7 )

Cross-section of a membrane
electrode assembly consisting
of Nafion 117 and electrodes
made of pure Pt (cathode) and
pure Ir (anode).
Courtesy: Fraunhofer ISE

PEM electrolysis

Catalysts
IrxRuyTazO2

V-I characteristics comparing the performance of

different binary and ternary unsupported
electrocatalysts for the OER.
T. Smolinka et al., Polymer Electrolyte Membrane (PEM) electrolysis in
Hydrogen and Fuel Cells: Fundamentals, Technologies and
Applications (Ed. D. Stolten), Wiley-VCH (2010)

Cell potential of PEM water electrolysis cell at high

current density (1 Acm-2) and 80oC.
() 0% Ta; () 10% Ta; () 20% Ta; () 30% Ta.
A.T. Marshall et al., Int. J. Hydrogen Energy 32 (2007) 2320 2324

PEM electrolysis

Catalysts: Research trends

Improvement of the electrocatalytic activity for OER using different binary

and ternary supported catalyst systems (metal oxides)
Use of stabilizing agents, e.g. conductive titanium sub-oxides
Reduction of metal loading of Pt-based catalysts for HER to values smaller
than 1 mgcm-2
Substitution of Pt as a catalyst for HER: e.g. use of nickel or cobalt
glyoximes as low-cost compounds which are stable in strong acidic media
Use of alternative catalysts synthesis methodologies (Adams fusion,
sputtering, sol-gel, sonochemistry)
Application of nanostructured thin film electrodes

PEM electrolysis

Current collectors

Hydrogen side: electrode potentials are close to zero; it is possible to use carbonbased materials such as carbon papers or felts as known in PEM FCs.

Oxygen side: graphite or carbon-based materials are not stable at the anodes
working potential. Carbon undergoes electrochemical oxidation at voltages > 0.9V
according to:
C 2H2O CO2 4H 4e

Instead of carbon, porous titanium structures made from titanium are mainly
used (main drawbacks: formation of oxide layers, high cost).

sintered Ti powder

sintered Ti felt

expanded Ti mesh

C-based paper

PEM electrolysis

Bipolar plates (cell-separators)

Requirements

High bulk electrical conductivity

Gas-impermeable (separates H2and O2 compartments)
Facilitate water flow and gas evacuation
High electrical conductivity and high surface conductivity
Resistant to hydrogen embrittlement
Stable in oxidizing environment
Low-Cost

Approach

Replacement of carbon (C) with titanium (Ti)

Development of low-cost dual-layer structure (e.g. C/Ti)
Application of alternative coating strategies
Unitized parts and laminate designs

PEM electrolysis

Bipolar plates (cell-separators)

PEM electrolysis

Stack design: efficiency/power consumption

Operating current density: 0.5 2 Acm-2 (1.7 - 2.1V)

Pressure: 0.8 20.7 Mpa
Current efficiency: up to 98%
Stack power consumption: 4.1 5.1 kWh Nm-3

PEM electrolysis

Stack design: lifetime

Courtesy: Hydrogenics

Thermal management is facilitated due to endothermic reaction (water recirculation)

High mechanical stresses (pressurized operation, pressure fluctuations at start/stop)
Degradation mechanisms:

membrane thinning
titanium embrittlement by hydrogen
corrosion/dissolution/agglomeration of catalyst and support
deterioration of seals

PEM electrolysis

System design

Small systems (< 1 Nm3h-1): 6-8 kWhNm-3

Large systems (> 10 Nm3h-1): < 6 kWhNm-3

Power conditioning unit

Feed water pump
(Low pressure) circulation loop for
oxygen side with heat exchanger,
water purification stage and gaswater separator
(High pressure) circulation loop for
hydrogen side with gas-water
separator
Hydrogen conditioning unit with a
demister (to remove droplets and
aerosols), heat exchanger and
condensate trap (to reduce dew
point to room temperature)
Water drain to recapture the water
transported via the membrane to the
cathode (electroosmotic drag)
Control and safety installation

PEM electrolysis

Advantages over classical (alkaline) technology

no corrosive electrolytes
good chemical and mechanical stability
high protonic conductivity
high gas impermeability
excellent gas separator
high current density at higher efficiency
reduced number of moving parts
easy maintenance
excellent partial-load range and rapid response to
fluctuating power inputs
compact stack design allowing high pressure operation

PEM electrolysis

Key benefits

Produces virtually no pollution when combined

renewable energy sources
Uses existing infrastructure
Uses fuel cell advances

Critical challenges

System efficiency and capital/feedstock costs

Integration with renewable energy sources
Design for manufacturing

PEM electrolysis

Major R&D needs

Develop of more durable and less expensive membranes

Develop of long-lasting membranes and corrosion resistance
interconnects (bipolar plates)
Develop of durable, low-cost and active anode electrocatalysts
Design of novel architectures for large-scale production
Balance storage and production rate capacity for variable
demand
Develop of flexible, scalable systems using low-cost materials
Increase reliability for high-temperature units

PEM electrolysis

Thank you!