Modeling of Advanced Alkaline Electrolyzers

MODELING OF ADVANCED ALKALINE
ELECTROLYZERS
(A system simulation approach)
2003
 ABSTRACT:
 The model is based on a combination of fundamental

thermodynamics .heat transfer theory and empirical
electrochemical relationships
 It can be used to predict the cell voltage .hydrogen
production, efficiencies and operating temperature.
 The model can be particular useful for:
1. System design.
2. Optimization of control strategies.
 Introduction :
 Hydrogen is often referred to as the energy carrier of the

future because it can be used to store intermittent renewable
energy (RE) sources such as solar and wind energy.
 The main objectives of these hydrogen projects was to test
and develop components , demonstrate technology and
perform system studies on two categories of systems:
1. Stand-alone power system (SAPS)
2. Hydrogen refueling stations (the hydrogen refueling
station at Munich airport)
 Photovoltaic (PV),wind energy conversion systems (WECS) weak
grid application
 Water electrolysis :
1. Alkaline system
2. Proton exchange membrane (PEM)
 There is a need for an electrolyzer model that is :

1. Suitable for dynamic simulation of such system.
2. With a relatively high level of details
3. Can be coupled to economic models that account for both
investment and operational costs.
 Technology :
 The electrolyte used in the conventional alkaline water

electrolyzers has been aqueous potassium hydroxide
 With solution of (20% -30%) because of the optimal conductivity
and remarkable corrosion resistance of stainless steel in this
concentration range.
 The typical operating temperature and pressure of these
electrolyzers are 70-100℃ and 1-30bar.
 Mono polar design :
The electrical connection of the individual cells
 Bipolar design:
The individual cells are lined in series electrically and
geometrically.
 Advantages of bipolar over mono-polar :
1. More compact than mono-polar

2. It gives shorter current paths in the electrical wires and
electrodes.
3. Reduced the losses due to internal ohmic resistance of the
electrolyte
4. Increases the electrolyzer efficiency.
 Disadvantages of bipolar
1. The parasitic currents that can cause corrosion problems.

2. The compactness and high pressure require relatively
sophisticated and complex system designs.
3. This increases the manufacturing costs.
 Nevertheless most commercial alkaline electrolyzers manufactured

today are bipolar.
 New advanced alkaline electrolyzer :
1. Operational cell voltage has been reduced reducing the unit

cost of electrical power and thereby the operation costs.
2. Increase the current density to reduce the investment costs.
 Problem:
1. Ohmic resistance increases with increasing current due to

increasing gas bubbling.
2. Increased over potentials at the anodes and cathodes due to
increasing current densities.
 How to overcome these problems :
1. New cell configuration to reduce the surface specific cell

resistance despite increased current densities .(zero gap cells
and low resistance diaphragms)
2. Higher process temperature (up to 160 c) low cell resistance
high electric conductivity.
3. New electro-catalysts to reduce anodic and cathodic over
potentials (mixed, metal coating containing cobalt oxide at
anode )
 Modeling
 The electrolyzer model presented is written as a FORTRAN

subroutine primarily designed to run with the simulation programs
TRNSYS and EES.
 But the model has also been designed so that it readily can be
integrated into other simulation programs (mat-lab)(Simulink)
 TRNSYS: TRANSIENT SYSTEM SIMULATION PROGRAM
with a modular structure.
 EES: engineering equation solar.
 Model description
 The decomposition of water into hydrogen and oxygen

can be achieved by passing an electric current (DC)
between two electrodes separated by an aqueous
electrolyte good ionic conductivity.
 Total reaction for splitting of water.
H2O (l) + electrical energy → H2 (g) + ½ O2 (g):
Anodic and cathodic reactions are:
Anode: 2OH− (aq) → ½ O2 (g) + H2O (l) + 2e−
Cathode: 2H2O (l) + 2e− → H2 (g) + 2OH− (aq)
 Properties of the electrodes in an alkaline solution :

1. Resistant to corrosion
2. Have good electric conductivity and catalytic
properties.
3. Good structural integrity
 Properties of the diaphragm :

1. Have low electrical resistance
(C-Pt) platinum activated carbon catalyst
 Thermodynamic model :
 Assumptions :
o max electrolyzer temperature of 100c
o hydrogen and oxygen are ideal gases
o water is an incompressible fluid
o the gas and liquid phases are separate
o standard temperature and pressure (25℃ and 1bar )
the change is Gibbs energy :

∆G =∆H – T.∆S:
(∆G) Change in Gibbs energy (∆S) Change in entropy
(T) Temperature (∆H) Change in enthalpy
At standard conditions the splitting of water is a non- spontaneous
reaction which means that the change in Gibbs energy is positive. (delta
G=237KJml-1)
 the emf for a reversible electrochemical process or the reversible

cell voltage :
Urev =∆G /z.F
(Urev) reversible cell voltage

(Z) = 2 No. of electrons transfered per reaction
(F) = 96485 C/mol.
→ The Thermo-neutral cell voltage:

𝑈𝑡𝑛 =∆𝐻/𝑧.F
→ At standard conditions 𝑈𝑟𝑒𝑣 = 1.299 𝑣 and 𝑈𝑡𝑛 = 1.482 𝑣
By increasing temp. 𝑈𝑟𝑒v decreases slightly while 𝑈𝑡𝑛 remains almost
constant
(𝑈𝑟𝑒𝑣 @ 80° 𝐶 = 1.184 𝑣, 𝑈𝑡𝑛 @ 80°𝐶 = 1.47 )
Increasing pressure increases 𝑈𝑟𝑒𝑣 slightly while 𝑈𝑡𝑛 remains constant
(𝑈𝑟𝑒𝑣 @ 30 𝑏𝑎𝑟 = 1.295 𝑣)
2) Electrochemical Model:
→ Fig: Typical I.U curves for an electrolyzer cell at high and low temp.
r
→ 𝑈 = 𝑈𝑟𝑒𝑣 + L
A + 𝑠 . Log (𝑡𝐴𝐼 + 1)
(𝑈) voltage
(𝑟) parameter related to ohmic resistance of electrolyte, 𝛺 𝑚2
(𝐴) area of electrode, 𝑚2
(𝐼) current, 𝐴
(𝑠) coefficient for over voltage on electrodes, 𝑉
(𝑇) coefficient for over voltage on electrodes, m2/A
( )
t2 t 3
t1 + + 2
→ U =U rev +
r 1 +r 2 T
I +s . log
T T
I +1
A A
→ The Faraday efficiency (The Current Efficiency):

The ratio between the actual and theoretical maximum amount of
hydrogen produced in the electrolyzer.
( I / A )2
nf = f
2 2
f 1+ ( I / A )
→ According to Faraday’s law, the production rate of hydrogen in an

electrolyzer cell
is directly proportional to the transfer rate of electrons at the electrodes
which in turn
is equation to the electrical current in the external circuit.
→ The total hydrogen production rate in an electrolyzer:
𝑛̇𝐻2 = ∫ 𝑓𝑛𝑐𝐼𝑧 𝐹
(𝑛̇) molar flow rate, 𝑚𝑜𝑙/𝑠
(𝑛𝑐) number of cells in series per stack.
→ The water consumption and oxygen production rates are simply
found from
stoichiometry 𝑒𝑞 (1):
𝑛̇𝐻2𝑂 = 𝑛̇𝐻2 = 2 𝑛̇𝑂2
→ The energy efficiency can be calculated from eq: (6) and eq: (8)
∫ 𝑒 =𝑈𝑡𝑛𝑈
→ const. temp. ↑ hydrogen prod. ↑ 𝑈 ↓ 𝑍𝑒
→ const. current density ↑ 𝑇 ↓ 𝑍𝑒
→ eq.(12) is only valid for systems where no auxiliary heat is added to
the system
( If added 𝑍 > 100% )
→ to calculate the overall performance of an electrolyzer system:
1- No. of cells in series and / or parallel per stack
2- No. of stacks per unit.
→ no. of cells in series → rated voltage
→ no. of cells in parallel → rated current ( 𝐻2 production )
→ total power = current × voltage
3) Thermal Model:
→ the overall thermal energy balance: (per stack)
𝐶𝑡𝑑𝑇𝑑𝑡 = 𝑄̇𝑔𝑒𝑛 − 𝑄̇𝑙𝑜𝑠𝑠 − 𝑄̇𝑐𝑜𝑜𝑙
(𝐶𝑡) overall thermal capacity of electrolyzer, 𝐽𝐾−1(𝑄̇𝑔𝑒𝑛) the internal
heat generation(𝑄̇𝑙𝑜𝑠𝑠) the total heat loss to the ambient(𝑄̇𝑐𝑜𝑜𝑙) the
auxiliary cooling demand
𝑄̇𝑔𝑒𝑛 = ∫ 𝑐 (𝑈 − 𝑈𝑡𝑛)𝐼 = 𝑛𝑐 𝑈𝐼 (1 − ∫ 𝑐 )
(𝑛̇𝑐) no. of cells in series per stack.
𝑄̇𝑙𝑜𝑠𝑠 =1𝑅𝑡( 𝑇 − 𝑇𝑎)
(𝑅𝑡) overall thermal resistance of electrolyzer, 𝑊−1𝐾
(𝑇𝑎) ambient temp.𝑄̇
𝑐𝑜𝑜𝑙 = 𝐶𝑐𝑤 ( 𝑇𝑐𝑤,𝑖 − 𝑇𝑐𝑤,0 ) = 𝑈𝐴𝐻𝑋 𝐿𝑀𝑇𝐷
(𝐶𝑐𝑤) thermal capacity of cooling water, 𝐽𝐾−1
(𝑈𝐴𝐻𝑋) overall heat transfer coefficient – area product for heat
exchanger, 𝑊−1𝐾
(𝐿𝑀𝑇𝐷) log mean temp. difference,

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MODELING OF ADVANCED ALKALINE

 The model is based on a combination of fundamental

 Hydrogen is often referred to as the energy carrier of the

 There is a need for an electrolyzer model that is :

 The electrolyte used in the conventional alkaline water

 Advantages of bipolar over mono-polar :

1. More compact than mono-polar

1. The parasitic currents that can cause corrosion problems.

 Nevertheless most commercial alkaline electrolyzers manufactured

 New advanced alkaline electrolyzer :

1. Operational cell voltage has been reduced reducing the unit

1. Ohmic resistance increases with increasing current due to

 How to overcome these problems :

1. New cell configuration to reduce the surface specific cell

 The electrolyzer model presented is written as a FORTRAN

 The decomposition of water into hydrogen and oxygen

 Properties of the electrodes in an alkaline solution :

 Properties of the diaphragm :

the change is Gibbs energy :

 the emf for a reversible electrochemical process or the reversible

(Urev) reversible cell voltage

→ The Thermo-neutral cell voltage:

→ The Faraday efficiency (The Current Efficiency):

→ According to Faraday’s law, the production rate of hydrogen in an

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