Overview of Alkaline Water
Electrolysis Modeling
« Paper Review »
Paper by:
Camilia Daoudi, Tijani Bounahmidi
Presented by:
Muhanad Raed Shweiter
Introduction
• The global shift away from fossil fuels is essential due to
climate change and resource depletion.
• Green hydrogen, produced via water electrolysis, presents a
clean and storable energy carrier.
• Alkaline water electrolysis (AWE) is a mature and cost-
effective technique for large-scale hydrogen production.
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Hydrogen Production Technologies
• Four major water electrolysis types: AWE, PEM, AEM, SOE.
Hydrogen Production Technologies
Alkaline water Anion exchange Polymer exchange Solid-oxide
electrolysis membrane membrane electrolysis
(AWE) (AEM) (PEM) (SOE)
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Hydrogen Production Technologies
• AWE and PEM are commercialized; AEM and SOE are still
under development.
• Each method has specific advantages and limitations regarding
cost, stability, and operational conditions.
• AWE uses low-cost, non-noble metal catalysts and alkaline
electrolytes like KOH or NaOH.
• Offers long lifespan (up to 60,000 hours) and lower capital
costs.
• Suitable for industrial-scale applications.
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Challenges in AWE
• Limited current densities compared to PEM.
• Gas crossover through the diaphragm.
• Slow dynamic response and ohmic losses in liquid electrolytes.
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Role of Modeling
• Modeling enhances understanding of system behavior and helps
optimize performance.
• Enables prediction of efficiency, heat management, gas purity,
and flow dynamics.
• Reduces costs and accelerates system design and scale-up.
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Primary goal of the paper
• Deliver a comprehensive understanding of the modeling
approaches governing AWE electrolyzers.
• Explain the underlying principles governing AWE electrolyzers.
• Focus on the equations used for two-phase flow modeling.
• Highlight key factors essential for constructing accurate and
effective AWE models.
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Basic concepts of AWE Electrolyzer
• AWE process is based on
the water splitting
technique, which utilizes
electricity to divide water
into its two main
components, hydrogen
(H2) and hydroxyl ions
(OH-)
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Structure of the AWE System
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Structure of the AWE System
Category Units
Power Supply AC source, Transformer, Thyristor Rectifier
Electrolysis Unit Electrolyzer Stack (Cathode, Anode, Separator)
Recirculation Centrifugal Pumps, Agitation Probe
Cooling Lye Cooler, Heat Exchangers
Primary & Secondary Gas-Liquid Separators,
Separation
Demister
Purification Hydrogen Cooler, Adsorbers, Palladium Deoxidizer
Storage Hydrogen Buffer Tank
Sensors, PRVs, Flow/Temperature Controls
Instrumentation
(implied in system)
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Models of AWE subsystem
Different physicochemical phenomena occur at each component
of the AWE cell, so each of these system components can be
considered as a subsystem as depicted.
AWE system components
Subsystem 1: Subsystem 2: Subsystem 3: Subsystem 4: Subsystem 5:
Cathode Anode Diaphragm Cathode Anode
compartment compartment
(Cathode- (Diaphragm-
Diaphragm) Anode)
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Electrode Subsystem Modeling
The electrochemical reaction at the electrode electrolyte boundary
occurs in different stages:
(i). Transfer of reagents from the liquid electrolytic to the electrode's
surface.
(ii). diffusion of reactive substances inside the pores of the electrodes.
(iii). electrochemical transformation on the catalytic sites of the
electrode: adsorption of reagents and products desorption.
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Electrode Subsystem Modeling
(iv). transfer of ions and electrical charges.
(v). diffusion of species inside the pores of the electrode towards
external surface of the electrode.
(vi). and species diffusion from the outer electrode's surface to the
electrolyte solution.
These different phases can be characterized by the equations listed
below, which describe the behavior of the porous electrode in AWE
electrolysis
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Electrode Subsystem Modeling
Ohm's law to the solid matrix, the electrical charge transfer in the
solid matrix material can be expressed as follow:
This flow of charges species is described by the Nernst-Planck
equation as follows:
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Electrode Subsystem Modeling
The Butler-Volmer equation serves as the basis for the expression of
the current density transfer:
This equation captures the physical significance of electrochemical
reaction kinetics at the electrode-electrolyte interface, including the
effect of concentration, temperature, and reaction rates.
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Separator Subsystem
• Functions: separate gases and conduct OH⁻ ions.
• Modeled using Fick's Law of diffusion.
• The diffusivity of ions in AWE via separator obeys Fick's law:
• It is clear that performance depends on porosity, thickness, and
tortuosity.
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Compartment Subsystem
• Compartments contains electrode and separator immersed in
electrolyte.
• The interaction of gas bubbles and liquid electrolytes forms a
two-phase flow system.
• The treatment of these two-phase flows model is based on the
Euler-Lagrange framework
• Key equations: Mass and momentum balances.
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Compartment Subsystem
• Compartments contains electrode and separator immersed in
electrolyte.
• The interaction of gas bubbles and liquid electrolytes forms a
two-phase flow system.
• The treatment of these two-phase flows model is based on the
Euler-Lagrange framework
• Key equations: Mass and momentum balances.
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Compartment Subsystem
• Euler
• Lagrange
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Whole System Modeling
• Stack operation involves:
• [1] Electrochemical models
The most frequently used method for displaying the electrochemical behavior is a
polarization curve. These models form the basis for modeling the electrolysis system.
To describe this, many authors have used the cell voltage (Ecell) modeling approach:
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Whole System Modeling
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Empirical equations
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Whole System Modeling
[2] Mass balance.
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Whole System Modeling
[3] Energy balance.
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Models developed for AWE
Prototypical I-U curves for an electrolyzer cell
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Models developed for AWE
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Previous models problems
• However, these terms and coefficients lack meaningful physical
significance, which can result in a discrepancy between the
predicted and actual system performance.
• To address this issue, some studies in the literature have
employed a more physical approach by incorporating the
principles of physicochemical mechanisms to describe the
electrochemical behavior of AWE electrolyzer
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Physicochemical-Based Models
These models incorporate:
•Pressure and temperature effects explicitly.
•Thermodynamic corrections using Nernst-type formulations.
•More accurate estimations of reversible voltage Erev, improving realism under
varying operating conditions.
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Physicochemical-Based Models
These models incorporate:
• Explicit use of Butler-Volmer and Tafel-type kinetics.
• Bubble coverage effects, which impact electrochemistry by altering effective
electrode surface area.
• Temperature and pressure influence on reaction rates and kinetics.
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Physicochemical-Based Models
These models incorporate:
• Physical representation of resistive losses through:
• Electrode/electrolyte/separator resistivity.
• Temperature dependence of conductivity.
• Effects of bubble coverage and void fraction on electrolyte resistance.
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Physicochemical-Based Models
This model incorporate:
• Modeling of mass transport limitations at the electrode surface.
• Concentration gradients for H2 and O2 at cathode/anode interfaces.
• Physically realistic estimates of losses from species diffusion.
And it's clear that moving from purely empirical curve fitting to physically
grounded Multiphysics modeling, enhancing both the accuracy and transferability
of simulations across different AWE systems and operating conditions.
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Gas Crossover Modeling
• There is a problem, known as gas crossover, poses a significant
challenge in alkaline water electrolysis systems. It refers to the
unintended mixing of hydrogen and oxygen gases due to diffusion across
the separator or dissolution and migration through the electrolyte. This
phenomenon compromises hydrogen purity, reduces system efficiency,
and introduces serious safety risks because hydrogen-oxygen mixtures
are highly explosive.
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Gas Crossover Modeling
• To overcome this, advanced gas purity models were developed that account for
operating conditions such as temperature, pressure, and current density, as well as the
physical behavior of gases in the electrolyte.
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Thermal Modeling in AWE
Key Contributions
• Ulleberg (2003) introduced a first-order nonlinear differential
model for thermal behavior:
• Captures internal heat generation (Qgen), heat loss (Qloss), and
cooling demand (Qcool).
• Does not include gas–liquid heat exchange.
• Hammoudi et al. (2012) extended the model:
• Added heat exchange with hydrogen, oxygen, and water (Qexch)
Accounted for electrode bubbling coverage and pressure effects.
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Thermal Modeling
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Two-Phase Flow Modeling
• Gas bubbles (H₂ and O₂) formed during electrolysis accumulate on
electrode surfaces, blocking active sites,this leads to:
– Reduced electrochemical reaction efficiency
– Increased ohmic resistance
– Poor mass transfer and temperature control
• Two-phase flow modeling is needed to understand and control this
gas–liquid interaction, especially for high-performance or high-
pressure AWE systems.
• Helps optimize cell design, flow channel geometry, and operating
conditions.
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Two-Phase Flow Modeling
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Simulation Tools
• The authors provide a list of
software they used to solve
the equations in their models,
which are typically complex
and require specialized tools
to handle. This list is
presented in the following
table.
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Research Gaps
• Need for integrated multi-physics models.
• Real-time simulation capabilities are limited.
• Ion & Gas Transport Existing models oversimplify transport across
electrolytes and diaphragms.
• Thermal Modeling Few models address complete system heat management
it must include components like pumps and coolant systems.
• Mass transport and impurity control are poorly represented.
• Models should include strategies for gas purity and impurity mitigation.
• Most models of Two-Phase Flow in Zero-Gap Cells focus on planar
electrodes; limited insights into porous media.
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Research Trends
• Improving the efficiency and stability of electrolyzers:
Researchers are working to develop new materials and designs for
alkaline electrolyzers that can improve their efficiency and stability.
• Developing methods to control and optimize the hydrogen and
oxygen production:
Researchers are investigating ways to control and optimize the
generation of hydrogen and oxygen gases to improve alkaline
electrolyzers' performance
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Research Trends
• Exploring the utilization of alkaline electrolysis for various
purposes:
Researchers are exploring the use of alkaline electrolysis for
various applications, including hydrogen production for fuel cells,
and renewable energy storage.
Overall, the research trend modeling focuses on finding ways to
improve alkaline electrolyzers' performance, efficiency, and
stability and expand their use in various applications.
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Advantages of the paper
• Provides a comprehensive review of modeling efforts for AWE,
including electrochemical, thermal, and two-phase flow aspects.
• Well-structured presentation of existing models' key equations
and parameters.
• Identifies clear research gaps, which is valuable for guiding
future work.
• Using tables to summarize the models is very helpful in this
paper, mainly for readers who are new to alkaline water
electrolysis.
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Disadvantages of the paper
• The paper gives a good summary of the previous research efforts,
but it does not introduce any original contributions from the
authors.
• Although the paper covers a broad range of topics, it provides little
comparative analysis between models, reducing its effectiveness as
a comprehensive review.
• The paper would be improved by including additional comparative
figures or schematic diagrams that clearly summarize the
differences between models. The current equations do not provide a
clear visual representation of the models.
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