PEM water

electrolysis
fundamentals
Dimitrios Tsiplakides
Hydrogen production
Encyclopedia of Electrochemistry, Volume 5: Electrochemical Engineering, Wiley (2007)
Production and consumption of hydrogen
Only 0.25% of
hydrogen produced
worldwide was
produced by
electrolysis
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 so-
called hydrogen
economy
H
Y
D
R
O
G
E
N

Hydrogen production
Hydrogen is fastest growing industrial gas
2015 Targets
*

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

capital cost of 1,500-2,500 /kW for industrial units and 4,000-5,000 /kW for micro-CHP
*
(FCH-JU)
Central
production
Commercial plants using
alkaline electrolysis have
operated at capacities
over 60,000 kg /day for
industrial chemical
processing
Renewable plants using
renewable feedstocks
(wind, solar, etc.) are
envisioned in longer term
Distributed
production
Produced at station to
enable low-cost delivery
Currently available using
grid electricity
Renewable
demonstration systems
using PEM electrolysis
already in place at select
locations
What is water electrolysis?
Electrolysis of water is the decomposition of
water (H
2
O) into oxygen (O
2
) and hydrogen
gas (H
2
) due to an electric current being
passed through the water.

2 2 2
H O H + 1/2O
Thermodynamics
2 2 2
H 1 2 286
o *
r
O H / O H kJ /mol + A = +
*
water is liquid
286 03 0 163
o o o
r
G H S ( . . T) kJ /mol A = A TA =
A = + =
2 2 2
1 2 0 163
o o o o
H O H O
S S / S S . kJ /mol K
Ideal gas enthalpy of
formation, kJ/mol
Ideal gas entropy,
kJ/molK
O
2
0 0.205
H
2
0 0.130
H
2
O (liquid) -286.03 0.069
Perry's Chemical Engineers' Handbook, Section 2.Physical and Chemical Data
A = + =
2 2 2
1 2 286 03
o o o o
H O H O
H H / H H . kJ /mol
G
o
corresponds to the
minimum share of H
o

which has to be applied
as work, e.g. electricity
(endothermic: energy has to be applied)
TS
o
corresponds to the
maximum share of H
o
which
can be applied as thermal
energy to the process.
Thermodynamics
The minimum necessary cell voltage to start water electrolysis is the reversible
(no losses in the process) potential:


n=number of electrons transferred (n=2)
F=Faradays constant (F=96487 C/mol)



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:





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

o
rev
G
V
n F
A
=

Example: at 25
o
C V
rev=1.23
V
o
th
H
V
n F
A
=

Example: at 25
o
C V
th=1.48
V
Thermodynamics
The importance of thermoneutral potential for water electrolysis


cell potential
The cell is heated by the excess
energy generated by the joule
heat caused by the overpotentials
V
rev
(1.23V)

V
th
(1.48V)

The cell will cool as the cell
dissipates the heat associated
with the entropy change,
irreversibly
V
th
is higher than V
rev
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):




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, V
rev
). In
this case, external heat is required to supply the remaining energy required (-S).
Example: electrolysis at 25
o
C:
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 V
rev
the higher is the current density and in
turn the production rate.
o
th
V H
G V
A
c = =
A
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 H
2

production price can be reduced
Thermodynamics
Effect of pressure

The equilibrium potential, E, is described by the Nernst equation:

E
o
Nernst potential at standard pressure (=G
o
/nF)

If we assume that the overall pressure is equal at both electrodes, the increase of E with
pressure is given by:




2
2 2
1 2
H O
/
H O
p
RT
V V ln
nF p p
o
=
1 2
1
/
RT
V (V V ) ln
nF p
o
A = =
Example: an increase in the overall pressure from 1 atm to 200 atm corresponds
to an increase in E by only 34mV (@ 25
o
C) and 48mV (@150
o
C)!
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 > V
rev
:

cat
overpotential at the cathode

an
overpotential at the anode
iR
A
ohmic losses within the cell and its components
R
A
area-specific ohmic resistance

an
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
).

rev cat an A conc
V V | | i R = + q +q + +q
Types of electrolyzers
Type Alkaline Acid
Polymer
electrolyte
Solid oxide
Charge carrier OH
-
H
+
H
+
O
2-
Reactant water water water water, CO
2
Electrolyte
Sodium or
Potassium
hydroxide
Sulphuric or
Phosphoric
acid
polymer ceramic
Electrode Raney Ni Pt Pt, Ir Ni-cermet
Temperature 40-90
o
C 150
o
C 20-150
o
C 700-1000
o
C
Types of electrolyzers
Overall reaction:
Half-cell reactions
Type Alkaline Acid
Polymer
electrolyte
Solid oxide
Charge carrier OH
-
H
+
H
+
O
2-
Cathode reaction
(HER)
Anode reaction
(OER)
2
2
2 2
2
H O e
H OH

+
+
2
2
2
1 2 2
OH H O
/ O e

+
+
2
2 2 H e H
+
+
2 2
2
1 2
2
H O / O
H e

+
+
2
2 2 H e H
+
+
2 2
2
1 2
2
H O / O
H e

+
+
2
2 2
2 +O H O e H

+
2
2
1 2 2 O / O e

+
2 2 2
H O H + 1/2O
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: 70-100
o
C 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)

+ +
2 2
2 2 2 H O e H OH

+ +
2 2
2 1 2 2 OH H O / O e
Classical water electrolysis
Alkaline electrolysis
Require cheap
electrodes
Cheap
construction
material
Low specific
production rate
Low efficiency
Large system
size
A
d
v
a
n
t
a
g
e
s

D
r
a
w
b
a
c
k
s

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


+
+
2
2 2 H e H

+ +
2 2 2
1 2 2 H O / O H e

2 2 2
HO H + 1/2O
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 m
2
)

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 m
2
and then 0.23m
2
per cell
involving a 200 kW module capable of
producing 55 m
3
h
-1
H
2
)
PEM electrolysis
Performance optimization
Components resistivity
Membrane thickness, ion-exchange capacity
Oxygen kinetics
cell
o
i
E ln i R
i
o
= E +| +

dif bipolar electrolyte contact
R R R R R = + + +

*
Current efficiency (or Faradaic efficiency):
molar H
2
rate production divided by (i/2F)
PEM electrolysis
Components
Components cost
Schematic of PEM electrolyser
showing the location of the components
Membrane Electrode Assembly (MEA)
Membrane
Anode and Cathode electrode

Gas diffusion Layer (Current collector)

Bipolar plates
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
PEM electrolysis
Proton exchange membrane

Supported Membranes (Dimensionally Stable Membranes, DSM
TM
)
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

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 (H
3
PO
4
doped)
BPSH
P
F
S
A

O
N
O Y O
x
y
X X O
N
N
O X
z
O
ADVENT TPS
PEM electrolysis
Proton exchange membrane: Performance


PEM electrolysis
Proton exchange membrane: Durability









Membrane degradation
F
-
release rate: 3.7 g/hr (<10 ppb)
Estimate lifetime: ~55,000 hrs
Indication of
membrane
degradation
PEM electrolysis
Catalysts
Mixture of catalyst and ionomer in order to enlarge the area of three-
phase-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 (RuO
2
) is the most active material for OHR; yet it is highly
unstable (the oxidation of RuO
2
to RuO
4
occurs at potentials more positive
than 1.387V)
Iridium oxide (IrO
2
) 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 (SnO
2
, TaO
2
, SbO
2
, TiO
2
, Ti
4
O
7
)


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








Cell potential of PEM water electrolysis cell at high
current density (1 Acm
-2
) and 80
o
C.
() 0% Ta; () 10% Ta; () 20% Ta; () 30% Ta.

A.T. Marshall et al., Int. J. Hydrogen Energy 32 (2007) 2320 2324
Ir
x
Ru
y
Ta
z
O
2
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)
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 carbon-
based 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:

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



2 2
2 4 4 C H O CO H e
+
+ + +
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 H
2
and O
2
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
Power conditioning unit
Feed water pump
(Low pressure) circulation loop for
oxygen side with heat exchanger,
water purification stage and gas-
water 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
Small systems (< 1 Nm
3
h
-1
): 6-8 kWhNm
-3
Large systems (> 10 Nm
3
h
-1
): < 6 kWhNm
-3

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!