POSTPRINT VERSION. The final version is published here: Makhsoos, A., Kandidayeni, M., Pollet, B. G.

, & Boulon, L. (2023). A perspective on increasing the efficiency of proton exchange membrane water electrolyzers– a review.
International Journal of Hydrogen Energy. CC BY-NC-ND Online ahead of print https://doi.org/10.1016/j.ijhydene.2023.01.048

A Perspective on Increasing the Efficiency of Proton

Exchange Membrane Water Electrolyzers– A Review

Ashkan Makhsoos*1, Mohsen Kandidayeni2, Bruno G. Pollet3,4, Loïc Boulon1

1
Hydrogen Research Institute (HRI), Department of Electrical Engineering and Computer

Science, Université du Québec à Trois-Rivières (UQTR), 3351 boulevard des Forges, Trois-

Rivières, Québec G9A 5H7, Canada

2
e-TESC Lab, Department of Electrical and Computer Engineering, Université de Sherbrooke,

2500 boulevard de l'Université, Sherbrooke, Québec J1K 2R1, Canada

3
GreenH2Lab, Hydrogen Research Institute (HRI), Department of Chemistry, Biochemistry and

Physics, Université du Québec à Trois-Rivières (UQTR), 3351 boulevard des Forges, Trois-

Rivières, Québec G9A 5H7, Canada

4
Hydrogen Energy and Sonochemistry Research Group, Department of Energy and Process

Engineering, Faculty of Engineering, Norwegian University of Science and Technology

(NTNU), NO-7491 Trondheim, Norway

* Corresponding author.

[email protected]

1
 ABSTRACT

Decarbonized hydrogen production using renewable energy sources and water electrolysis is

perceived as a promising solution for a sustainable future. The efficiency of PEMWEs relies on

several multiphysical aspects and even a slight increase in their efficiency may change the future

of sustainable energy routes. Hence, this paper reviews the most compelling research on increasing

PEMWE efficiency, which is one of the main pillars for the advancement of this technology.

Various publications, including chemical engineering, materials, mass transfer, energy transfer,

electrical control, power generation, and hybrid systems, are considered. From the electrolyzer

power sources (renewable energy, hybrid, power to gas), inputs (power regulation, water

temperature, pressure, ambient temperature), and stack, to components design, control strategy,

and new hybrid designs have come under scrutiny in this manuscript. Finally, five essential

recommendations are given as the pathways for future studies on PEMWE efficiency.

Keywords: PEMWE; HyPro; Electrolyzer Efficiency; Membrane electrolyzer; Hydrogen

2
 Nomenclature

Renewable Energy Source RES Transport Layer TL

Hydrogen Production HyPro Gas Diffusion Layer GDL

Proton Exchange Membrane PEM Membrane Electrode Assembly MEA

Water Electrolyzer WE Temperature Swing Adsorption TSA

Fuel Cell FC Porous Transport Layer PTL

Photovoltaic PV Catalyst Coated Membrane CCM

Power-to-Gas PtG Mass Transport Limitation MTL

Catalyst Layer CL Charge Transfer Coefficient CTC

Computational fluid dynamics CFD Maximum Power Point Tracking MPPT

Fuzzy Logic Control FLC Dual Organic Rankine Cycle DORC

Oxygen Evolution Reaction OER Ground Source Heat Pump GSHP

Platinum Group Metal PGM Balance of Plant BOP

Stainless Steel SS Fuzzy Logic Control FLC

3
1. INTRODUCTION

One of the most practical alternatives to traditional energy, which mainly depends on fossil fuel,

is renewable energy sources (RESs) [1]. They are much less detrimental to the environment. The

key downsides of renewable energy are its reliance on the weather, its incapacity to store, and its

availability when needed. In this regard, power-to-gas (PtG) is undoubtedly one of the best

environmentally friendly solutions for storing renewable energy [2, 3], which is dominating the

market [4]. In the literature, PtG is reviewed from various points of view, such as technology [5],

economics [6], market and portfolio effects [7], electrolysis and methanation status [8],

thermochemical water splitting cycles [9], and solar energy [10]. In recent years, hydrogen

production (HyPro) has drawn the attention of policymakers, industries, and individuals. The

production and use of hydrogen are also on the rise worldwide [11, 12], with technologies such as

hydrogen vehicles, hybrid cars, and other green systems [13]. Researchers predict that HyPro from

RESs will be critical in transforming the global energy system into a sustainable energy system by

2050 [14-16].

Electrolysis is now a crucial technology for HyPro, forming the basis of future energy systems

as an energy carrier. Most PtG systems use the electrolysis process to produce hydrogen.

Electrolyzers are rapidly expanding in the market to meet the world's clean energy demand,

although they need additional durability, efficiency, and performance improvement [17]. Brynolf

et al. studied the production costs of modern fuel (electrofuels or PtG) for transportation systems.

Based on a review of more than 130 articles, they concluded that HyPro with electrolysis could be

reliable in both small and large-scale applications if capital costs and stack life are considered [18].

This study reviews all of the struggles in increasing the PEMWE's efficiency. After this short

introduction, in the second section, the PEMWE's importance, advantages, industrial status,

4
literature review, drawbacks, and possible solutions are reviewed. Section 3 discusses; operational

conditions and the stack component's role in increasing efficiency, system configuration, models,

and energy control. Finally, in the third section the combined systems and hybrid sources are

discussed. Section four explores future perspectives, and section five gives a conclusion.

2. Polymer Electrolyte Membrane Water Electrolyzer (PEMWE)

PEMWE is an efficient and clean method for generating H2 from water by electrolysis. Proton

conduction, separation of the produced gases, and electrical insulation of the electrodes occur in a

zero-gap cell equipped with a solid polymer electrolyte in a stack section. From this reaction

among cathode and anode sides and catalyst layers, H2 and O2 are generated [19]. PEMWE has a

considerable potential of HyPro from RES by its privileges to play an essential role in reducing

greenhouse gas emissions in the hydrogen sector. Studies show that PEMWE may eliminate

conventional steam methane reforming from the field of HyPro by 2050 [20].

2.1. Popularity of PEMWE

PEMWE has been attracting significant attention in recent years due to its superiority over other

green HyPro methods, and its excellent potential to connect to RESs. These clean and free sources,

such as solar and wind, are tremendously dynamic. This challenging operational condition makes

the HyPro complicated and inefficient because the energy intensity is intermittent. However,

unlike alkaline water electrolyzers, PEMWE quickly reacts to the fluctuations of RESs, withstand

high-temperature ranges, performs well in variable power input modes, operates at higher current

densities, and has high energy conversion efficiencies [21, 22]. PEMWE can either be directly

coupled with other sources in proper circumstances or use maximum power point tracking (MPPT)

tools by a regulator (DC/DC).

5
Moreover, PEMWE is more straightforward than the alkaline type since it delivers high-quality

gas and has lower maintenance requirements. Therefore, the operational, maintenance, and repair

costs of HyPro are reduced, and energy efficiency is increased using PEMWE [23]. Mohammadi

and Mehrpooya reviewed several studies on the performance of various electrolyzers linked with

a variety of RESs. The positive aspect of such research is to optimize the electrolyzer's connection

with RESs [24].

It is also shown in [25] that PEM electrolyzers can generate hydrogen and oxygen as a byproduct

at up to 350 bar pressures with small additional power consumption, which is attractive for

hydrogen storage usage or applications that use pressurized hydrogen. In addition, depending on

the material used, PEMWE can maintain high efficiency while operating at high pressures [26]. A

PEMWE can produce ultrapure hydrogen with higher than 99.999% purity, and even a fuel cell

can be fed by it [27].

The benefits of the PEMWEs, such as less corrosivity [28], flexibility, high proton conductivity

[29], thin proton exchange membranes [30], relatively low operating temperature [31], and low

computational complexity [32], are explained in numerous articles. In this regard, decarbonization

[33], fast response [34], and fast cold start [35] are also noticeable.

PEMWE modules require less space than alkaline ones (about 20%) [31]. Hence, they have a

higher density (smaller footprint) than their rivals. On a small scale, it is efficient, clean, and has

good compactness. Increasing the electrolyzer's scale to enormous sizes [32]. The produced

hydrogen in the output can also be compressed to reduce transport storage costs [36].

In a nutshell, fast response to the power source, high differential operating pressure, high current

densities, high power densities, hydrogen purity, high production rates, compact design, and the

capability of working in variable operating conditions are the upper hands of PEMWE in its

6
industrial success [59]. Currently, PEMWEs are in a state of development with various limitations.

A complete list of these limitations and disadvantages is discussed in section 1.4.

2.2. The embracement of PEMWE by industry

As mentioned in the previous section, due to the ability to connect to new energy sources,

PEMWEs are becoming more popular year by year. The first commercial version was sold in 1978

[37]. However, the competition among companies and even countries is in progress to set a new

record for HyPro nowadays [38]. Mittelsteadt expressed, "today at least five companies are at or

near the launch of MW electrolyzers systems" in 2015 [39], and now, every forward-looking

company knows the only path for the future is RES." The capability of PEM electrolyzers to

rapidly change the power consumption has a desirable feature for frequency stability," said

Alshehri et al. [44]. Figure 1 illustrates these concepts and the industrialization process of

PEMWEs. Several key events have occurred along the path to PEMWE improvements, including

obstacles, critical successes, and significant advances. According to this Figure, the modern design

of PEMWE has caused models and control strategies to become more sophisticated after the 19th

century. The flowchart shows that efficiency is among the highest importance for future scenarios,

same as durability and cost.

7
 Figure 1 Improvements, turning points, and challenges of PEMWEs

Table 1 illustrates the size, output pressure, energy demand, and model of nearly all PEMWE

providers. From this table, the United States of America, France, Germany and China are the

greatest PEMWE providers. It is also noticeable that there are of course other laboratory and

industrial manufacturers, however only the census of prominent companies has been conducted.

Furthermore, The largest operating unit of PEMWE using 20 MW RES is implemented in

Bécancour, Canada (Quebec) by the Air Liquide company and Cummins technology. This unit

ensures the low-carbon hydrogen supply for industrial use and mobility in North America by up

to 8.2 tons of HyPro per day [40]. Cummins Inc. also claims that they have constructed the largest

PEMWE in the USA at the Douglas County Public Utility District in Washington [41]. Thus, it is

the beginning of the competition for manufacturing more outstanding PEMWEs. Shortly after,

Linde announced that the worlds largest PEMWE (24-megawatt) will be established at the Leuna

chemical complex in Germany and then some months later a 35-megawatt in Niagara Falls, New

York [42, 43], and Air liquid unveiled a 30-MW project by 2023 [44].

Table 1 Origin, model, sze and energy requirement of PEMWE providers

Brand (Company) Model HyPro Required Average power Maximum Country

power consumption Output
pressure

8
 200-250 1.4-1.7 55
(Nm³/h) (MVA) (kWh/kg)
400-500 3.2 54
Cummins HyLYZER (Nm³/h) (MVA) (kWh/kg)

435 (PSIG)
1000 7 51
(Nm³/h) (MVA) (kWh/kg)
4000 23 51
(Nm³/h) (MVA) (kWh/kg)
M 104-417 0.53-2.2 59
(Nm³/h) (MVA) (kWh/kg)

USA
G 200-600 120-230 (9.17-6.94) 116
Proton on site (cc/min) (VAC) (Wh/L) (PSIG)
G4800 4.7 205 – 240 6.17
(L/min) (VAC) (Wh/L) 200
S 9.4-18.8 205-240 6.7 (PSIG)
(L/min) (VAC) (kWh/Nm³)
Plug Power EX-425D 200 1 49.9
(Nm³/h) MVA (kWh/kg)
EX-2125D 1000 5 49.9 580
(Nm³/h) MVA (kWh/kg) (PSIG)
S 027-1.05 NA 6.1 200
(Nm³/h) (kWh/Nm³) (PSIG)

Norway/ Denmark/US
C 10-30 85-236 68.9 - 64.5
(Nm³/h) (kVA) (kWh/Nm³)
M 1,698-4,920 NA 4.5
(Nm³/h) kWh/Nm³
MC 264-492 NA 4.5
Nel (Nm³/h) (kWh/Nm³)

435 (PSIG)
H 2-6 22-55 7.3-6.8
(Nm³/h) (kVA) (kWh/Nm³)
ELYTE 10-260 100-1680 4.9
(Nm³/h) kVA (AC) (kWh/Nm³)
Elogen Open Power Min. 500 Min. 3.2 5

France
(Nm³/h) MVA (AC) (kWh/Nm³)
Multi MW Min. 2000 Min. 13 4.8
Systems (Nm³/h) (MVA) (AC) (kWh/Nm³)
AREVA H2Gen E 5-120 40-960 5.7 -4.8 507.6
(Nm³/h) (kVA) (AC) (kWh/Nm³) (PSIG)
PURIFIER 1.2 7.3
(Nm³/h) (kVA) (DC)
CUSTOMIZE 2.8 17.5
R (Nm³/h) kVA (DC)
SUPPLIER 7.6 47.3
(Nm³/h) (kVA) (DC)
580 (PSIG)

STORAGER 19.4 120.6

(Nm³/h) (kVA) (DC)
NA

PURIFIER 100 0.8 4.6

(Nm³/h) (kVA) (DC)
Germany

HIAT CUSTOMIZE 1.9 11.1

R 100 (Nm³/h) (kVA) (DC)
SUPPLIER 4.8 30.1
100 (Nm³/h) (kVA) (DC)
HYP 5-20 35-102 1450 - 580
(Nm³/h) (kVA) (DC) (PSIG)
HCS 420-2100 2-10 4.8
(Nm³/h) (MVA) (kWh/Nm³) 435
ME450 210 1 4.8 (PSIG)
H-TEC SYSTEMS (Nm³/h) (MVA) (kWh/Nm³)
S 0.22-1.1 1-5
(Nm³/h) (kVA)(AC) NA NA

9
 ME 46.3-210 500-1.707
(Nm³/h) (kVA) (AC)
10 75 5.4 (kWh/Nm³)
(Nm³/h) (kVA) (DC)
30 205 5.2 (kWh/Nm³)
(Nm³/h) (kVA) (DC)
gEl 60 400 5.2 (kWh/Nm³)

580 (PSIG)
PEM (Nm³/h) (kVA) (DC)
Igas MD 100 660 5.4 (kWh/Nm³)
(Nm³/h) (kVA) (DC)
160 1050 (kVA) 5.4 (kWh/Nm³)
(Nm³/h) (DC)
320 2070 (kVA) 5.3 (kWh/Nm³)
(Nm³/h) (DC)
100 up to 70 NA
Siemens Silyzer 2000 (kg/h) (MVA)
21 (kg/h) 1.25 (MVA) 507.6 (PSIG)
AUKEWEL/ANBO ABS-XQ-06 300 (ml/min) 180
S (VA) (AC)
BEIJING CEI HGPM 300-1500 NA
TECHNOLOGY (ml/min)
Zhongrui ZRA3 50 (ml/min) 30 (VA) (DC)
QLSC-H4 4 22
Saikesaisi (Nm³/h) (kVA) (DC)
QLC 60-1000 (45-540)
(ml/min) (VA) (DC)

China
Cawolo 150-600 150-600 70 -300
(ml/min) (VA) (DC)

NA
Eason Industrial GH 2-100 (12.88-469.2)
Engineering Co., (Nm³/h) (kVA) (DC)
Ltd
NA

ZDQ-12 12 90
PERIC (Nm³/h) (kVA) (DC)
CNDQ-(5-12) 5-12 40-120
(Nm³/h) (kVA) (DC)
SENZA SZPE 300-1200 80-260
(ml/min) (kVA) (DC)
ITM Linde N/A N/A N/A Germany
Electrolysis
Swiss hydrogen PEM 1 6 435 PSIG Switzerland
electrolyser (Nm³/h) (kVA) (AC)
Hydrogenics Corp HyLYZER 1-5000 6.7-25000 Canada
(Nm³/h) (kVA) (AC)
ITM Power Hgas 0-2000 0-10 UK
(Nm³/h) (MVA)
NA

GreenHydrogen.dk A 30-90 135-418.5 Denmark

ApS (Nm³/h) (kVA) (AC)
McPhy Energy S.A. NA NA NA France
Giner, Inc NA NA NA USA

2.3. State of the art, obstacles and possible solutions regarding PEMWEs

Carmo et al. examine the new and old challenges relating to electrocatalysts, solid electrolytes,

current collectors, separator plates, and modeling efforts. The structure of PEMWE is analyzed,

materials are discussed, and the challenges are noted [23]. Shiva Kumar and Himabindu's paper
10
contains new studies, graphical comparisons, and PEMWE models [23]. Ayers's publication in

"Current opinion in electrochemistry" is about the potential of PEMWEs and their associated

components. A description of the performance of a typical electrolyzer can also be found in this

paper [45].

HyPro using PEMWE can be tracked in review papers from 2004 when Zoulias et al. published a

review article on WE with a deep insight into various techniques of that time and its history from

1789 [46]. Almost all review articles on electrolyzers are included in this section; most of these

publications discuss PtG [47, 48], different methods of HyPro [49-55], and HyPro by RES [56-

58]. For instance, Berstad et al. [59] review liquid hydrogen as a prospective energy carrier. They

studied the impact of battery limits on hydrogen value chain studies and identified the knowledge

gaps that need to be addressed. They also mentioned that it needs a comprehensively bottom-up

approach to understand better the pros and cons of different hydrogen energy carriers. Shan et al.

[60] have reviewed long-duration energy storage technologies. They mainly focused on projects

that were commercially mature or industrialized. This work also compares modularity, long-term

energy storage capability, and average capital cost with varying durations. Insights gained from

this study can assist the development of long-duration energy storage projects, inspire use cases

for different long-duration energy storage technologies, and be used to create a foundation for

future relevant modeling and decision-making studies. Some highlight chemical and fundamental

topics, which are the basis of PEMWE [61, 62]. HyPro in a particular country is also the subject

of two publications [63, 64]. Some authors propose increasing the efficiency approach in a

particular component or process, intensification [65], the definition of energy efficiency coefficient

[66], verification of existing HyPro systems, and PEMWE models [67-69]. Other articles consider

varying points of view, such as exergy attention [49], techno-economics [70, 71], economics [72],

11
transportation [73], special applications in space [74, 75], and specific supplements (geothermal

[76], wastewater [77]). The number of all review papers that PEMWE is the main or part of their

concerns is presented in Figure 2. From 2014-2018 and 2010-2014, the number of reviews has

increased by over twofold and fivefold compared to 2018-2022, respectively, which illustrates that

PEMWEs are becoming more popular. The main concern of all these publications is demonstrated

in Figure 3, as no publication has not directly reviewed all possible ways of enhancing PEMWE

efficiency.

12
 Figure 2 Number of review papers on PEMWE and its associated components

Figure 3 The main concern of review papers

Based on the studies conducted on PEMWEs, their development challenges are mainly attributed

to production costs, component durability, and high efficiency. Decreasing electrolysis costs is

expected to make PEMWE technology more welcome [78]. Most publications point out the cost

of platinum group metal (PGM) materials, such as iridium (Ir) and platinum (Pt), as the major

13
disadvantage, and researchers explore solutions [79, 80]. The PEMWE cost has experienced a

dramatic reduction in recent years due to mass production and scaling up. Additional savings will

be feasible based on technology advancements and manufacturing developments, similar to the

PEM fuel cells pathway [81]. In addition, Young et al. prove that existing fuel cell materials and

hardware can also be applied to PEMWEs, in particular cases adhering to the associated limitations

[82]. Therefore, the existing fuel cell pathway can be tracked and transferred to the younger and

rapidly growing PEMWEs. The evolution of PEMWE technology involves both process and

material advancement, which are currently under investigation by scientists and engineers

worldwide. Two significant system costs are manufacturing the PEMWE stack and the balance of

plant (BOP). BOP expenses would account for about two-thirds of the total system cost. The share

of these costs can be different for various electrolysis scales [83-85]. The final price of the stack

mainly depends on cell power density, manufacturing process, membrane and its catalyst, the

thickness of the transport layers. Figure 4 shows the general range of prices mentioned in the

explored references. From this figure, the costliest part is the heart of the electrolyzer. Catalysts

and membranes have an integrated design in new generations of PEMWE (Catalyst Coated

Membrane (CCM)). However, if they were designed separately, they would be even more

expensive. Secondly, various layers designed for mass and gas transfer are called Porous Transport

layers (PTL). Finally, BPs are other costly parts of a stack.

14
 Figure 4 Approximate shares of Influential components on a stack price

PEMWE materials and constructions are expensive, and their prices also fluctuate

drastically. As illustrated in Figure 5, the PGM cost, a primary catalyst in PEMWE, fluctuates

wildly. HyPro's large-scale by PEMWE faces severe obstacles because of the iridium demand and

potential bottlenecks [86].

15
 Figure 5 PEMWE catalysts (PGM)prices [87]

In addition to the cost, another criticism of the PEMWE is its acidic environment, which is

responsible for corrosion, degradation, and reduced lifespan. [71]. The mechanisms of the

individual component degradation are investigated by Feng et al. They showed significant failure

in the PEMWE components (the catalyst/catalyst layer, membrane, current collector, and bipolar

plate) [88]. The strategies to mitigate the degradation are also presented. Some methods to increase

electrocatalyst stability are as follows: adding inert oxides, forming or single-phase alloy of binary

or ternary catalysts, catalyst morphology tailored to the application, and increasing the adhesion

between the catalyst layer and membrane via unique methods. They divided the membrane

degradation into mechanical, chemical, and thermal degradation. Some solutions, such as reducing

the creep characteristics of PFSA membranes, membrane reinforcement, or modification by

incorporating reinforcement materials in polymer chemistry, are advised to be adopted. Current

collectors and bipolar plates are susceptible to degradation mechanisms, such as corrosion,

16
embrittlement, and passivation. Furthermore, current collectors may be damaged by improper

clamping force. BPs are coated by stainless steel (ss), advanced materials and compounds (e.g.,

metal nitride), and a new deposition to minimize the coating defects and decrease the component's

expenses significantly. Furthermore, Stiber et al. [89] index that BPs and ss meshes can be used

instead of the expensive porous structure of PTLs. Tajuddin et al. have shown how recycling can

tackle specific acidic electrolyte problems with remarkable stability and relatively cheap prices

[90]. In addition, Khatib et al. completely covered the material degradation of PEMWE

components in a review paper and strategies for improving cells' durability and efficiency [91].

Shirvanian & van Berkel have published an exciting mini-review on the PEMWE

limitations. The study is mainly about the performance and durability of different components.

They considered long-term implementation and short-term strategies for decreasing costs and

significantly improving lifetime [92]. Another problem listed for PEMWE is the water inlet. It

must be purified for the current membranes, which can be detrimental to its reputation. Since

desalination and water treatment are necessary before the initial process, more cost, technology,

and time will apply consequently [51]. However, ongoing studies show efforts to make

electrolyzers available to consume a more comprehensive range of H2O [93]. The main concern

of papers that studied PEMWE problems are listed in Table 2, and the possible solutions suggested

by the authors are also mentioned.

17
Table 2 summarizes the main indicated obstacles and their solutions in the discussed papers

Obstacle

manufacturing
Durability

Operating
Perspective Solutions and suggestions Ref.
Cost

Catalyst [79]

separation, recovery, and recycling

PGM materials replacement of conventional PGM [90]

metal catalysts with non-noble

metal catalysts

material reduction, substitution, [80]

Techno- scale-up, and learning by doing

economic large-scale, high-temperature [71]

analysis (TEA) technologies

source availability and

uninterrupted energy supply

material and process development [81]

Carbon paper as anode PTLs [82]

Avoid Contact between membrane

and graphite

Technology Mitigation and alleviating strategies [88]

and catalyst, membrane, current

performance collector, bipolar plate

18
 Adding inert oxides and forming a

solid solution [91]

reinforcing materials such

as polymer fibers

Coating the bipolar plate,

improving materials

reinforced membranes, [92]

overpotential operation,

stable support and coating

materials

chlorine evolving reaction, [51]

Input water utilization of ion-selective

membrane

ion crossover in direct saltwater

electrolysis, preventing cathode [93]

fouling and considering HER-

catalyst crystal structure,

morphology, and loading effects

All in all, any efficiency increase in the electrolyzer will help raise the HyPro and reduce the cost

of the process. Consequently, a lower cost, higher capacity, and more durable PEMWE system

would be a technological leap that can lead to the higher application of the zero-carbon hydrogen

for various applications. In this regard, no review article has explicitly looked at increasing

PEMWE efficiency.

19
In this paper, several articles are reviewed to comprehensively define methods for improving the

electrolyzer's efficiency. Numerous efforts have been made to enhance the PEMWE efficiency,

durability, and affordability. The roots of most of these methods offer material science or

chemistry solutions to study and improve electrolyzer fundamentals. However, some suggest

energy management or integration with other systems. Furthermore, some studies work on the

flow system with a fluid mechanic approach (Figure 6).

3. Increasing PEMWE energy efficiency

Considerable efforts have been made to enhance the efficiency of PEMWEs. The roots of

these studies for increasing PEMWE efficiency are represented in Figure 6. From this figure, It is

evident that the four main science branches that can increase PEMWE efficiency are; Chemistry,

Material science, Electrical engineering, and Fluid mechanics. It also illustrates that the studies on

PEMWE are in three main areas: in-situ, ex-situ, and as a black box. First, in the in-situ research,

a part of PEMWE or an action is studied in its original place. Second, ex-situ is the investigation

of a section, component, or phenomenon out of the PEMWE and separately from the other parts.

Finally, from the black box point of view, the researcher studies the PEMWE as a whole system

and analyzes it with inputs and outputs. Lamy and Millet have studied the rate of energy efficiency

by collecting various coefficients. Their work focuses on the most common electrolyzers near

ambient temperature [66]. Other authors also employ process investigation, exergy calculation,

and alternative methods to increase efficiency. Burton et al. have reviewed various methods,

including hybrid coupling technology, magnetic fields, light energy, ultrasonic fields, and

pulsating electric fields, to realize their effect on the efficiency of HyPro using RESs [94].

20
 Figure 6 Various science branches that can increase different parts of PEMWE efficiency

3.1. Operation conditions

The main electrolysis process in a PEMWE takes place in its stack, where operation occurs by gas

interaction and mass transfer. [95, 96]. The influence of different operating conditions on the

performance of PEMWEs has been investigated in different papers and is shown in Table 3.

According to this table, several studies have focused on the effect of operational conditions and

input currents on the PEMWE efficiency. Moreover, other factors have been influential, including

temperature, pressure, flow rate, and current density. In this regard, Fritz et al. [97] focused on the

21
simulation of capturing the performance of a PEMWE model operating at high current densities.

Their study entailed predicting membrane proton transport and accurately studying the mass

transport and ohmic losses under electrolyzing conditions. Marangio et al. analyzed different new

objectives for PEMWE performance. First, a break-even value of the operating pressure in the

range of 30-45 bar was considered. Second, a new design with a metal foam layer as the support

at the anode side of MEA was successfully tested and validated [98]. Toghyani et al. studied

different design parameters and operating conditions to analyze the performance of PEMWE at

the steady-state condition with a three-dimensional numerical model. They have done one of the

most comprehensive research by surveying temperature, pressure, gas diffusion layer (GDL)

thickness, and membrane thickness. At a voltage of 1.65 V, temperature varies from 373 K to

403 K, the maximum HyPro from 1.9 × 10−4 to 2.2 × 10−4 mol/m3. GDL change from 0.2 mm to

0.5 mm decreased current density from 0.426 A/cm2 to 0.40 A/cm2. Thickening membrane from

50 to 200 μm caused a drop of current density from 0.32 to 0.16 A/cm2. Operating pressure

variation from 5 bar to 20 bar led to higher open-circuit voltage and the partial pressure of different

species responsible for reducing the charge transfer rate and, consequently, the inferior

performance of the PEMWE [99].

In [100], the influence of temperature, pressure, and flow rate in two different cell designs (with

and without flow channels on the anodic side) was presented. Five different PTL structures were

also investigated by analyzing the polarization curves. Lickert et al. observed significant

differences in the performance between the two cell configurations. The electrolyzer performance

without a flow field was with lower pressure and temperature, and consequently, the flow rate

increased. However, they observed significant losses for incomplete removal of oxygen gas

induced by anodic PTL. Finally, they announced that the transport properties related to porosities

22
and particle/fiber diameters as PTL characterization and the in-plane and through-plane

permeabilities should be measured to characterize PTL structures for PEMWE properly. A

uniformly distributed heat, mass, and charge system is explained by Olesen et al. [101]. They

studied a high pressure and high current density operation of PEM electrolysis cells using a

dynamic flow approach. The effect of gravity has been examined by Choi et al. [102]. They studied

different parameters by the orientation of the cell, and the gravity impact on the electrolyzer

performance was explored. It was concluded that the single serpentine channel affected the

performance at high current density (about 8.3% more than the quintuple serpentine channel).

Moreover, the two-phase flow regime of water and oxygen in this channel and the PTL varied with

the cell orientation. It was also noticed that it did not affect the performance of the PEMWE cell

with the quintuple serpentine channel because its active areas did not vary with the cell orientation.

Table 3 operating conditions and their influence over the performance of the PEMEW

Operating conditions

Main study Result/Suggestion Ref.

Temperatu

Transport
Pressure

Current

Water transport Calculation of electro-osmotic drag [95]

coefficient, mass flow rate equation

of discharged water with hydrogen

in a cathode

Bubble Observation with Synchrotron [96]

formation and radiography

new transport pathways

23
 porous

structures

Zero prediction of the ohmic losses, [97]

dimensional maximizing the conductive contact

simulation areas

Manufacturing new activity should aim at a [98]

pressure of about 30–45 bar and

higher temperatures

Thermal and Best size of membrane, GDL, [99]

electrochemical catalyst for highest performance in

performance the sample

the in-plane and through-plane [100]

Anodic PTL permeabilities should be measured

in order to properly characterise

PTL structures

Heat and electrochemical performance [101]

charge parameters for obtaining the highest

transport in the accuracy

anode and

membrane

The pattern of high operating temperature and low [102]

anode channel flow rate reduce the activation and

24
 and effect of ohmic losses, and bubble coverage

gravity on the catalyst should be reduced

Two influential operating parameters of PEMWEs are pressure and temperature because they

affect various components [103, 104]. It has always been a question for designers and researchers

about the relationship between temperature, pressure, and maximum efficiency in different

systems. Should the operating pressure or temperature be higher, or an external process is

necessary for compaction? Tjarks et al. tried to find the answer about PtG systems with electrolyzer

pressure levels up to 20 bar. They studied the overall PtG plant's energy demand optimization,

considering compression and temperature swing adsorption (TSA). They concluded that a

particular optimum pressure exists for various operating conditions in the electrolyzer, which

depends on the stack's current density and the hydrogen storage pressure [105]. Some authors

expressed how the high-pressure PEMWE operation eliminates the need for external compression

in the HyPro process. Saebea et al. showed the advantage of delivering hydrogen at high pressure

with a more negligible effect on performance and low power requirement by simulating the

PEMWE based on an electrochemical model [106]. Scheepers et al. investigate the capability of

PEMWE membrane for efficiency improvement [107].

A mini-review of the high-pressure PEMWE system until 2014 can be found in the introduction

of Bensmann et al.'s paper [108]. Then, three possible thermodynamic models are energetically

evaluated in this work. The models are named pathways and are compared by balances for energy,

entropy, and mass. Finally, they mentioned the importance of this evaluation in decreasing the

costs and lessening the process, especially compacting the gas, as they studied PEMWEs up to 40

bar. Kim et al. predicted high-pressure PEMWE behaviour for gaining the advantage of a new

generation of large-scale electrolyzers by developing a one-dimensional dynamic model. They

25
studied voltage-current relations, overvoltages, water and gas permeation through the membrane,

1-D profiles of two-phase flow, temperature, concentration in the anode and cathode channels, and

profile over the MEA [109]. In 2021, Afshari et al. worked on a mathematical model of PEMWE

(a combination of electrochemical, and fundamental thermodynamic relations) [110]. They studied

the crossover phenomenon, water transferring mechanisms, and diffusion concentration. Their

final goal was to improve electrolyzer efficiency by controlling voltage loss, so the contribution

of electrodes, BP, and membrane resistance to electrolyzer performance was examined. They have

also investigated the influence of membrane thickness, cathode pressure, and temperature on the

anodic hydrogen content. So, they showed a significant reduction in hydrogen crossover from

cathode to anode due to a thicker membrane, whereas a larger cathode pressure will result in an

increased rate of crossover as the pressure difference between anode and cathode channels

increases, at a current density of 10,000 A/m2 results in 85% and 3% contribution of concentration

and activation over potentials, respectively.

3.2. Stack components

A stack primarily consists of the membrane, electrodes, catalyst, TLs , and BPs. A general view

of a cell from a PEMWE stack is shown in Figure 7. However, thanks to new research and cutting-

edge technology in unique modern designs, some components can be added, and some can be

changed or removed.

A. Membrane

The membrane is one of the stack components in the heart of the PEMWE cell. Its superior

performance will increase system efficiency. This part can be developed by replacing more

appropriate materials [111, 112] or using new electrochemical and physicochemical techniques

26
[113]. The coated membrane with catalysts, such as Iron(Fe) and Nickel (Ni) [114] porous titanium

[115], decreases the level of corrosion and increases the efficiency and durability [116].

Figure 7 PEMWE stack components

B. Catalyst

The Catalyst Layer (CL) in CCMs is another important PEMWE cell component. Currently, almost

all PEM electrolyzers use expensive PGM catalysts. They are expensive, and their degradations

are costly [117]. So, replacing them with low-cost [118], earth-abundant [119] non-precious

catalysts, such as molecular catalysts [120], metal cobalt phosphide (CoP) [121], MoS2 based

materials [122] and [Mo3S13] clusters anchored to N-doped carbon nanotubes [123], seems

reasonable. Iridium, Titanium, and Platinum compounds, as well as new versions of these

27
compounds, offer substantial improvements through the use of cutting-edge technology. For

example, iridium core/shell catalysts via galvanic exchange [124], nano-size IrOx catalyst with

high activity and stability [125], N–TiO2 nanofibres [126], or simply applying aerogel supports to

them [127].

Performance and durability at the cell level are not only affected by individual components but

also by fabrication methods. In addition, the parameters during fabrication also matter, impacting

the CL morphology [128, 129]. Alia et al. examined the effects of ink and ultrasonic spray

variables on CL properties, PEMWE performance, and durability. These parameters include the

ionomer content, solid concentration, solvent ratio, pump rate, and drying temperature. It was

found that kinetic performance was greatly affected by changes in ionomer quantity or dispersion.

As a result of increased ionomer concentrations and poor ionomer incorporation (catalyst-ionomer

segregation), the kinetics have been slowed, likely because the ionomer limits access to the Ir sites.

Besides, inconsistencies in catalyst layer thickness adversely affected ohmic loss, possibly by

reducing catalyst layer-PTL contact and increasing contact resistance [130]. For enhancing the CL

engaging and optimizing catalyst service even at high current density, transport resistance should

fall, and as a result, protonic and electronic conductivities rise [131]. It applies to electrolytes, and

their concentration will help their conductivity and increase their performance [132].

C. Gas Diffusion Layers

The next layer in PEMWE is the GDL. There is a lengthy research background [133] about it, a

vast improvement potential [134, 135], and studies on reducing its costs [136]. Accumulating

oxygen gas in PEMWE transition layers is a severe obstacle to achieving higher efficiencies. For

facilitating mass transport and increasing electrical conductance, a porous layer is ingrained in the

design of PEMWE, which is named PTL [137]. Research is still ongoing in this area to raise the

28
benefits of PTL [138]. Lee et al. have collected these studies and focused on PTL mass transport

losses in PEMWE to improve efficiency [139]. PTL development can diminish mass transport

losses, increase catalyst utilization and minimize the ohmic and kinetics losses of the PEMWE

[140].

A common problem in the flow of the PEMWE cell potential in high current density is called

the mass transport limitation (MTL). It decreases PEMWE efficiency by crippling transport in the

PTL. Panchenko et al. studied this effect on mass transfer processes comprehensively with

neutron-based imaging (neutron visualization techniques). They observed different in-situ

stoichiometries during the absorption of polarization curves. The importance of their study lies in

the optimized and efficient cell design [141]. In their publication introduction, Kim et al. have

brought a valuable review of PTL and CL techniques and materials until 2022. They presented a

new method of PTL and CL combination. They described it as tailoring the CL interfacial contact

in a PEMWE with bilayer titanium mesh PTL [142]. Ojong et al. have a compelling discussion

about predicting the PEMWE cell operation without a flow channel in PTL. They developed this

subject by studying coupled momentum, heat, and mass transport phenomena on a semiempirical

non-isothermal model [143]. Parra-Restrepo et al. studied the effect of the PTL and CL properties

on the mass and charge transfer in a PEMWE. They demonstrated that the PTL optimal outlet

depends not only on the operational condition of the PEMWE but also on the thickness and the

electrical conductivity of the CL. Based on this fact, they proposed a new model for the constriction

resistance between the CL and the PTL. [144].

D. Bipolar Plate

The last key element of the PEMWE is the BP (Bipolar Plate). This multi-functional component

uniformly distributes air and liquid, manages electrical current from cell to cell, controls heat, and

29
prevents gases and coolant leakage [145, 146]. They must have the least interfacial contact

resistance and high resistance counter corrosion to withstand the operational conditions within the

stack. Furthermore, a coating layer may also be necessary for BPs [147]. These detailed

considerations have made a relatively expensive part out of BP [148].

On the other hand, cost reduction of stack components in PEMWEs is a priority nowadays. So,

inexpensive materials coated with anti-corrosive layers can be desired to replace conventional BPs,

reduce cost, and hopefully increase performance [149-152]. Taner et al. (2019) performed a

prototype HyPro study using PEMWE, and the result shows that this system can produce H2 about

4.5 times more efficiently than the other systems. PEMWE with a magnet (Cr-C Coated SS304

BP) shows higher efficiency than the bare one [153]. As a result of advances in manufacturing

technology and 3D printing, electrolyzers, BP, and some integrated components are now being

produced [154].

E. Charge transfer in cell components

Investigating the Charge Transfer Coefficient (CTC) is essential in anticipating electrolyzers'

current-voltage characteristics. Furthermore, this estimation provides insight into the electrode

properties. Biaku et al. studied the temperature dependency of the oxygen electrode CTC of a

commercial PEMWE stack [155]. Tijani et al. evaluated the operating temperature effects on the

CTC and its consequences on the operating voltage of PEMWE. Their study is essential in PtG

systems where activation overpotential plays a crucial role in the operating voltage. Their study

results show that CTC's value increases at higher operating temperatures. However, it enhances

the anode more significantly than cathode electrodes. In addition, it was observed that pressure

does not significantly affect CTC at each electrode [156]. In the next step, they investigated the

effect of exchange current density and CTC on PEMWE performance and its polarization. They

30
demonstrated that CTC needs are lower in higher exchange current density, so less activation

overvoltage and, subsequently, lesser operating voltage systems are required. In simpler terms,

using overvoltage in PEMWE will be more efficient, and all the excess energy capacity can be

used in this design. They also completed studies on the relation between temperature and CTC,

primarily effective on the oxygen electrode [157]. Table 4 demonstrates different solutions for

improving PEMWE performance, and the viewpoints of different studies are also explained.

Table 4 different ways for efficiency enhancement by each of the stack components

Component Ref.
membra

CL

TL

BP

Focus Results or Effects

Solid acid high proton conductivity at [111]

temperatures above 130 °C

Nafion properties high-pressure operating [112]

(Review)

Degradation issues Mitigation/ Better [113]

Hot pressing treatment performance and stability

catalyst-coated increaseperformance and [114-

membranes durability 116]

ultra-low catalyst Insights on the degradation [117]

loading mechanism

IrO2/TNO anode low cost and efficient [118]

catalyst

31
Earth-Abundant efficient and stable [119]

Electrocatalysts

Molecular catalysts tolerate high acidity [120]

Cobalt phosphide potential pathway for [121]

(CoP) commercial applications

low-cost, non-precious

MoS2 -based catalyst reasonable and promising [122]

[Mo3S13]2 clusters Cost reduction [123]

anchored to N-doped high-performing and stable

carbon nanotubes

Iridium Core/Shell emphasize the [124]

manufacturing feasibility

Nano-size IrOx cost-effective, [125]

outstanding activity for

oxygen evolution reaction

(OER) and stability

N–TiO2 Nanofibres High Efficient HyPro [126]

SnO2:Sb aerogel OER Better activity and stability [127]

Reducing anode maximizing catalyst [131]

catalyst layer proton- utilization at the high

and electron-transport current density

resistances

32
Electrolyte increasing electrolyzer [132]

Concentration efficiency

GDL review improving process [133,

efficiency 134,

137]

modified titanium calculate the porosity [135]

porous matrix

Transport perspective visualize the morphology [138]

Radiography, CT and oxygen transport

Mass Transport Losses minimize small capillary [139]

effects

and reduce large slug

formation

Neutron spectroscopy cell visualized in-situ [141]

Tailoring catalyst with Maximize interfacial [142]

titanium mesh contact area

Channel-less PEMWE costs advantage, mass [143]

cell transport constitutes

Mass and charge Optimal performance [144]

transfer

Pressure and velocity pressure drops diagonally, [145]

distributions

33
 Design, material, cost the coating layer is [146]

necessary to protect the

substrate

pH value, titanium Improve the adhesion of the [147,

coatings, plasma coating, Stable 148]

processing

Electrochemical the formation of a very [149]

Evaluation, Niobium stable, low

Corrosion Resistance porosity, the protective

oxide layer

Additive manufacturing possibility to design new [150]

and more complex flow

distribution channels

Coated stainless steels Corrosion resistance [151]

Carbon-coated stainless solution for the large-scale [152]

steel application

Cr-C Coated SS304 more efficiently and [153]

economically

all-in-one bipolar compact and efficient [154]

electrode

3.3. System function, configuration, control, and energy management

34
PEMWE has also been studied from other perspectives, considering system control, energy, and

configuration efficiency analyses. Preliminary studies on PEMWE efficiency have encountered

severe obstacles such as electrode pressure increase, electrode destruction, membrane melting,

membrane drying, overheating, or membrane rupture [158]. Zhang et al.'s design with a

thermodynamic and electrochemical outlook improves the system's overall performance, avoiding

irreversible losses. Interestingly, they expressed how the efficiency of their developed

configuration was higher than the conventional system, which directly released redundant heat into

the environment. PEMWE efficiency increases by surging the impact of the heat exchanger and

working temperature. In contrast, the efficiency is reduced by the increase in the electrolyte

membrane's thickness and the inlet water flow rate [159].

Koponen et al. studied control and energy efficiency in a commercial PEMWE system powered

by PV. They proved that wise pressure selection and control of PEMWE operation could minimize

consumption and maximize the real HyPro. They doubled the hydrogen outlet pressure and

observed that the electrical energy consumption did not significantly increase. However, the

specific energy consumption of the stack has increased significantly. In addition, they concluded

that attention to the PEMWE system's dynamic control would prevent accelerated cell degradation

[160]. A standard evaluation method for the performance of electrolyzers is to focus on fluid flow.

The fluidic phenomena that occur continuously in an electrolyzer can be modeled with Energetic

Macroscopic Representation (EMR) viewpoint [161]. Computational Fluid Dynamics (CFD) is a

known branch of fluid mechanics that equips researchers with numerical analysis and algorithms

to simulate the whole or part of PEMWE. For instance, using CFD, Upadhyay et al. provided a

deep insight into the flow pattern factors by assessing the anode flow field hydrodynamic behavior.

They considered the velocity value of the inlet and outlet port configuration in a new circular

35
PEMWE design. Furthermore, their findings helped the understanding of a uniform velocity

outline, maintenance of the desired temperature, reduced pressure drop, and active removal of

oxygen bubbles effectively. [162].

Olivier et al. developed a new model using the bond graph tool for improving PEMWE entire

system design for green HyPro, considering its exposure to intermittent electrical sources [163].

Martinson et al. also focused on RES nature and the current interrupt method on the

electrochemical characterization of PEMWE. They announced that increasing the working current

density and temperature decreases concentration losses [164].

Another solution proposed to increase system efficiency is using control strategies to protect the

electrolyzer against overvoltage, ensure input capacitors in dynamic operations, manage ripples

current and voltages, and increase reliability, durability, and efficiency [165, 166]. For instance,

Parache et al. observed a rise in ohmic resistance, titanium mesh corrosion and passivation, and

mass transport limitations. These effects seem to increase by triangular current ripples[167].

Various parameters can be determined by accurately modeling the PEMWE [168-177]. Dang et

al. [178] have represented a high-differential pressure PEMWE zero-dimensional steady and

dynamic model with high accuracy by calibrating a 0-700 bar pressure electrolyzer at different

cathode pressures and temperatures. Some unclear parts of previous models, such as the

concentration overpotential in the voltage composition, the cathode water flow problem, the

double-layer, and mass transfer lag effects, are also considered in their study.

Load modeling is essential for control goals, increasing system efficiency, and improving

performance [179-182]. Yodwon et al. reviewed PEMWE various load modeling with a control

approach and their comparison [183]. Keow and Chen used an automated adjustment approach to

establish an online proportional-integral control. In simple terms, they achieved the desired current

36
output by automatically adjusting the voltage applied to the PEMWE. The PEMWE inlet is a

nonlinear voltage and current, so its properties need to be investigated and controlled. They

evaluated and compared two tuning methods, Ziegler–Nichols and phase margin [184]. Other

authors, such as Fuzzy Logic Control (FLC), relied on water temperature to control and optimize

the PEMWE system, such as Fuzzy Logic Control (FLC) [185]. Wirkert et al. mainly focused on

heat management and how it affects PEMWE efficiency. They developed a high-performance

modular PEMWE system operation, dynamic high-pressure HyPro.

Moreover, the process water was experimentally validated regardless of heat management. They

claimed that future industrial-scale PEMWE stacks with optimized media flow homogeneous

operation conditions over a wide dynamic pressure range can be constructed using their presented

design approach. At the same time, a high degree of modularity provided complete flexibility for

individual system design [186].

Caparros Mancera et al. proposed a logic control design to maximize efficiency by evaluating

operational factors, observing the environment, and quality testing. The BoP is also considered in

power engineering. They tried to find a meaningful relation between performance and minimal

BoP in PEMWE [187].

3.4. Different Sources and Hybrid Systems

The efficiency of systems can sometimes be increased by integrating multiple electrical sources to

ensure a non-stop operation or by combining two or more configurations for maximum effect. This

section presents publications that meet these criteria. One of the advantages of PEMWE is

production despite intermittent electrical sources and accepting RES as the power source.

However, increasing the system's capability to connect this type of electrical current can

significantly raise its efficiency [188, 189]. Since most designs of PEMWEs operate with low

37
voltage and high current, converters using strategies such as LLC resonant can play a vital role in

integrating electrolyzer with a power source [190].

PEMWEs are the most well-known sources of HyPro power supply from RES. If they are assumed

as the primary power source, as shown in Figure 8, power network and individual batteries are

overcharged in some terms. Hence, the overpower of powerline, standalone batteries, and even

active consumers can turn into green hydrogen. PVs most often supply PEMWEs and therefore

electrolyzers' performance in this arrangement is consistently attractive [191]. Optimal coupling

approaches have been proposed by Yang et al. to improve the HyPro efficiency using a strategy

called direct coupling and increasing leakage resistance [192]. Some authors researched particular

combinations with PEMWE, such as concentrating solar plants [193], Photovoltaic Thermal (PVT)

[194], and PV directly coupled with PEMWE [195].

38
 Figure 8 Different sources and systems that can be combined with PEMWE

In recent years, hybrid RESs are becoming prominent in the energy sector for achieving more

sustainability, especially in standalone systems. So their integration with PEMWE is the subject

of new research [196]. As RES’s capacity factor is usually low, combining different sources will

be helpful. One of the successful scenarios of hybrid sources for PEMWEs is the combination of

wind turbines and PV arrays [197]. Zaik & Werle [198] have published an experimental

methodology review about PEMWE HyPro with RES. However, the main body of their paper is

about a PEMWE running with wind and solar in Poland. Their system produces 158.1 (cc/min)

hydrogen with an average efficiency of 69.87%. So, wind energy is another renewable source of

power for PEMWE [199]. This continuous energy source will increase the efficiency of HyPro.

Seyam et al. worked on optimizing a multi-objective hybrid RES supplied by solar panels, wind

turbines, and an absorption cooling system. They expressed that they achieved more than 65% of

39
energy and exergy efficiency [200]. Geothermal is another renewable source that can be combined

with PEMWE [201]. This technology brings both fresh water and hydrogen simultaneously. These

systems usually use a flash-binary geothermal and Organic Rankine Cycle (ORC) [202]. Alirahmi

et al. [203] have equipped ORC-PEMWE system with a lithium/bromide absorption refrigeration

cycle. The most influential parameters in their multi-generation system outputs are: geothermal

fluid mass flow rate, geothermal fluid temperature, ORC turbines inlet temperature, and evaporator

pinch-point. In some studies on power optimization of the geothermal flash systems with Dual-

pressure Organic Rankine Cycle (DORC), hydrogen generation performance in the PEMWE is

also investigated [204, 205]. Mehrenjani et al. [206] used liquefied nature gas (LNG) for the stream

as a heat sink. Using this method configuration combined with a PEMWE leads to HyPro and

liquefied it through a Claude cycle. Their introduced system produces up to 106.8 kg/h of

hydrogen, which can be raised to 154.95 (kg/h) due to optimizations.

According to some research, the overall efficiency of systems can be increased by merging them.

Furthermore, hydrogen is often generated along with other products in these systems [207]. For

instance, Marefati & Mehrpooya polygeneration system based on PV, PEMWE, PEMFC, and

thermoelectric device electrical efficiency is 53.3%, it provides the electrical, thermal and cooling

demand [208]. A combination of PEMWE and PEM Fuel Cell (PEMFC) seems to provide

sustainability of energy and temperature [209, 210]. Pirom & Srisiriwat [211] used this

combination and Photovoltaic for a residential house with a compelling overall system efficiency

between 1.75% and 7.66%. Freshwater as a byproduct of PEMFC was also available for the net-

zero emission residential house. Several proposed system produce fresh water, cooling or heating

along side with hydrogen using solar heliostat [212], parabolic solar collectors [213, 214],

geothermal power [215, 216], solar plus geothermal [217], solar plus wind plus geothermal [218],

40
biomass [219] for renewable electricity generation. Moltames et al. expressed that the results of

this system optimization were a 22.32% and 8.61% increase in energy and exergy efficiency,

respectively. Moreover, the cost rate of the entire system was decreased by 6.65% [220]. Armas-

Calderón et al. introduced a hybrid system consisting of a PEMWE, a thermoelectric generator,

and a dual-fuel engine. They showed that the overall system would have better exergetic efficiency

by integrating this hybrid system. After obtaining positive results, the optimal operating conditions

of each subsystem and their behavior were analyzed by varying the effective parameters on their

performance [221]. Some systems are more complex and need multi-criteria analysis [222-225].

Zoghi et al. designed a novel biomass-driven multi-generation system to simultaneously produce

power, heating, cooling, and hydrogen. They employed a thermoelectric generator, PEMWE, a

modified Kalina cycle for power and cooling production. Then they investigated their system from

energy, exergy, exergoeconomic, and environmental approaches, which sounds better than other

systems. However, there was no clear result to compare original subsystems without this

combination, which is necessary for professional conclusions [226]. Table 5 shows various

systems integrated with PEMWE, and the total performance, efficiency, cost, or function has been

changed. These inventions will give modern energy systems a higher level of flexibility, especially

in zero-carbon or low-carbon systems.

Table 5 Hybrid PEMWE systems with their properties

System
Achievement Ref.
integrated

with PEMWE

41
 Energy and [209

PEMFC temperature ,

sustainability, 210,

energy and 220]

exergy

efficiency

improvements,

and cost

reductions

PEMFC High efficiency, [211

+ Net-zero ]

Solar PV emission

residental,

Freshwater by-

product

Dual-fuel [221

engine ]

High exergy

efficiency
Thermoelectri

c generator
Compared to [226

other system, ]

42
modified exergy, energy,

Kalina-LNG exergoeconomi

c, and

environmental

approaches

sound better

cooling cycle Enhance the [222

of scramjet exergy and ]

efficiency, fuel

consumption

Dual organic Hydrogen cost [223

Rankine cycle and ]

equipped with environmental

an impact per unit

ejector exergy are

refrigeration improved

loop, a within 49.18%

biomass and 34.58%.

gasification Total cost

process decreased.

43
 Energy and [224

exergy ]

ground source efficiency is

heat pump acceptable also

GSHP improve the

flexibility of the

energy system

19.1% increase [225

in H2 ]

Solar thermal production,

overall

electricity

production by
Thermoelectri
recovering the
c generator
waste heat

4. Future perspectives

The previous chapter mentioned that increasing PEMWE energy efficiency depends upon different

scientific disciplines, so improvements in any of these areas will improve PEMWE efficiency.

However, multidisciplinary studies also made significant impacts. According to Figure 9 and the

PEMWE trajectory, efficiency, durability, and cost are three main domains that should be

considered in future studies.

44
• Although there has been some progress, further study of the new chemical compounds for

catalysts remains essential.

• Material science is expected to make the most remarkable contributions to increasing the

efficiency of electrolyzers, meaning new designs of the electrolyzer and its components

interfaces can be made with modern materials, such as nanomaterials. The studies of

membranes, electrodes, TLs, PTLs, and BPs, are highly recommended.

• The study of independent cases with unique circumstances, as demonstrated in several

articles, is strongly suggested in control and the studies on PEMWE operational

conditions, since each situation has its formula to thrive and be most effective.

• PEMWE technology in renewable energy storage is in its infancy and has much potential.

So it is a valuable recommendation for future scientific investigations and environmentally

sustainable energy systems. Another practical recommendation is to study hybrid

renewable sources for continuous HyPro in further details.

• Some systems can be integrated to boost efficiency and reduce waste, as was discussed in

the last chapter. Therefore, future studies should utilize all available capacities to

maximize the entire system's efficiency.

45
Figure 9 Future trends of PEMWE for increasing the efficiency

46
5. Conclusions

Hydrogen will undoubtedly play an essential role in the zero-emission energy system of the future.

Electrolysis is a valuable technology used as an energy carrier generator, forming future energy

systems to cross the age of fossil fuels and take advantage of the zero-carbon energy system. The

PEMWE is considered one of the best instruments for HyPro from RESs due to its reliability.

Although the technology is still in its infancy, many improvements are needed to increase

durability, performance, and efficiency. Therefore, it seems necessary to give experts in various

branches of knowledge a general idea of the situation to determine their capabilities for increasing

PEMWE efficiency. In this regard, different concepts of boosting PEMWE efficiencies, such as

chemistry, materials, mass and energy transfer, electrical control, power sources, and hybrid

systems, are reviewed in this manuscript. Each mentioned concept is explained by summarizing

the performed studies in this line of research and development and interpreting their results and

discussion. Lastly, five research axes are introduced as the guidelines for future endeavors to

enhance the efficiency of PEMWEs.

47
ACKNOWLEDGEMENTS

This work was supported in part by Natural Sciences and Engineering Research Council of Canada

(NSERC) [RGPIN-2018-06527]

48
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