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Materials development and prospective for protonic ceramic fuel cells

Article in International Journal of Energy Research · October 2021

DOI: 10.1002/er.7371

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 Materials Development and Prospective for Protonic Ceramic Fuel Cells

Idris Temitope Belloa, Shuo Zhaia, Qijiao Hea, Chun Chenga, Yawen Daia, Bin Chenb, Yuan

Zhangb,*, Meng Nia,*

a
Department of Building and Real Estate, Research Institute for Sustainable Urban Development

(RISUD), The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China

b
Institute of Deep Earth Sciences and Green Energy, College of Civil and Transportation

Engineering, Shenzhen University, Shenzhen 518060, China

* Corresponding author: [email protected] (Y. Zhang);

[email protected] (M. Ni)

Abstract

Protonic ceramic fuel cells (PCFCs) are considered a potential and more efficient upgrade to

conventional solid oxide fuel cells (SOFCs). This is predominantly due to their capacity to operate

efficiently at low and intermediate temperatures and their quality of non-fuel dilution at the anode

during operation. This review presents a detailed exposition of the material development strategies

for the major components of PCFCs (i.e., electrolyte, cathode, and anode) and how they differ

from the traditional SOFCs. Credible science backed recommendations for the synthesis and

fabrication of PCFCs materials are discussed. In the end, the opportunities, challenges, and future

directions for P-SOFCs are buttressed.

Keywords: Protonic ceramic fuel cells; cathode; anode; electrolyte; Solid oxide fuel cells

1
 1.0 Introduction

1.1 General overview of O-SOFC and H-SOFC

The past decades have witnessed a progressive surge in global energy demand. The increasing

world population and fast-paced urbanization have contributed a great deal to this high global

energy demand. Consequently, the emissions associated with the increasing energy consumption

have triggered a continuous and unfavorable change to the global climate. Hence, it is of

paramount importance to seek an environmentally friendly, clean, and sustainable energy

alternative. Renewable energy sources are considered a potential solution to the menacing

consequences of global warming on our planet. Some of the widely explored renewable energy

sources reported in the literature are solar [1,2], hydroelectric [3,4], wind [5,6], geothermal [7,8],

and tidal energy [9,10]. Nevertheless, due to many constraints ranging from the intermittent nature

of these common highlighted renewable energy sources to their peculiarities to different

geographical locations, as described in [11], make the quest for the development of reliable and

large-scale energy conversion and storage technologies a worthy objective. Fuel cells are highly

promising energy conversion technologies that convert chemical energy directly to electrical

energy with low emission and high efficiency. They are electrochemical systems just like batteries

but continue to generate electrical energy supply so long as there is no disruption in fuel and air

supply. Fuel cells are of different varieties, and they can be distinguished based on the type of

electrolyte used. Table 1 illustrates the different types of fuel cells developed, their operation

temperatures, power outputs, and electrolyte type. Among the different fuel cell types developed,

solid oxide fuel cell (SOFC) is the most promising for stationary applications with great potential

to replace conventional thermal power plants.

2
Table 1: The different types of fuel cells with their various distinct features.
Fuel Cell Electrolyte Operation Power Output Efficiency Catalyst Ref.

Temperature

Alkaline fuel cell Potassium hydroxide 60 – 120℃ 10 kW – 100 kW 35 – 70 % Platinum [12,13]

Phosphoric acid fuel Phosphoric acid 150 – 200℃ < 200 kW 40 – 80 % Platinum [14]

cell

Proton exchange Polymer membrane 50 – 80℃ 50 – 250 kW 40 – 50 % Platinum [15,16]

membrane fuel cell

Direct Methanol Fuel Polymer membrane 50 – 130℃ 100 MW – 1 kW 20 - 55 % Platinum [17]

Cell

Molten carbonate fuel Molten lithium or ≈ 650℃ 10 kW – 2 MW 60 – 80 % Nickel [18]

cell potassium carbonate

Solid oxide fuel cell Ceramics 500 – 1000℃ kW - MW > 60 % Nickel and [19–22]

Perovskites

SOFCs are ceramic-based energy conversion systems peculiarly characterized by the direct

conversion of chemical energy to electrical energy with low emissions and high efficiency [23].

Some of the advantages of SOFCs over other fuel cell types are fuel flexibility, lower overpotential

losses, higher efficiency, and relatively low cost. SOFCs are high temperatures (usually, 800 –

1000 ℃) operating electrochemical conversion systems that could be used for stationary power

generation (i.e., either centralized or distributed power generation source) in homes and other

areas. The high temperature is needed to enable fast oxygen ion conduction through the dense

electrolyte and fast reaction kinetics at the electrodes, especially the oxygen reduction reaction

(ORR) at the cathode. However, such a high working temperature also shows several drawbacks

[24]. The thermal cycling between room temperature and working temperature may cause

substantial thermal stress at the interfaces between different layers due to thermal expansion

3
coefficient (TEC) mismatch, which can severely decrease the performance and durability of SOFC

[25]. From a thermodynamics point of view, the maximum theoretical efficiency of fuel cells also

decreases with increasing temperature, thus, a too high working temperature is not favorable for

the energy efficiency of fuel cells. In addition, high working temperature requires complex and

costly thermal management systems and balance of plant (BOP), which raises the overall system

cost and hinders the practical applications of SOFC [26]. Hence, it is critical to developing SOFCs

that can operate at low to intermediate temperatures (usually in the range of 300 - 750 ℃ ) [27].

Previous studies have explored and expounded on SOFC components to achieve a cell that can

operate at an intermediate and even low temperature [21,28–35]. Some of the strategies prescribed

and investigated are the improvement of the electrolyte by using a super-thin (i.e with low ohmic

resistance) and the development of high-performance oxygen ion-conducting electrolytes,

particularly the doped ceria electrolytes, Gadolinium doped Ceria (GDC), and Samarium doped

Ceria (SDC)[29,36–40]. Another highly efficient strategy is to introduce mixed conductivity into

the electrodes such that they can effectively and simultaneously conduct electrons and ions [41–

44]. The advantage of this is that the ORR which often takes place at the triple phase boundary

(TPB) can be extended to the entire surface of the catalyst particles. These strategies have been

quite helpful as evident from myriads of earlier studies reported [45–51].

The cathode is one of the key components to improve to achieve efficient medium and low-

temperature operating SOFCs. This is because, it is the site where electrocatalytic ORR takes

place, and it influences the stability and durability of the cell. Extensive research has been done to

improve the performance, stability, and durability of cathode materials, particularly in oxygen ion-

conducting O-SOFCs. Zhou et al. [52] reviewed the progress in improving the popular

Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) perovskite oxide cathode material that was first reported by Shao

4
and Haile in 2004. BSCF was one of the first reported perovskite oxide materials with an excellent

performance at intermediate operating temperatures [53]. Pelosato et al.[54] reviewed over 250

articles highlighting the relevance of cobalt-based double perovskites for intermediate operating

solid oxide fuel cells and particularly singling out Pr-, Nd-, Sm-, and Gd-based cobalt-containing

layered perovskite oxides as promising candidates for intermediate-temperature SOFCs. Ding et

al. [26] also reviewed the use of Ruddlesden-Popper perovskites in intermediate-temperature

SOFCs due to their excellent catalytic activity towards ORR and high stability at low and medium

operation temperatures.

SOFCs can be classified into oxygen ion-conducting SOFCs (O-SOFCs) and proton-conducting

SOFCs (P-SOFCs) depending on the nature of charge carrier(s) in the ceramic electrolyte. Most

of the mainstream research in SOFCs is focused on the O-SOFCs in which oxygen ion is the charge

carrier in the electrolyte[55,56,65,66,57–64]. Numerous research works have been done in

improving the performance, stability, and durability of O-SOFCs with remarkable progress being

made, particularly in the improvement of the electrode activities of cathode materials for O-SOFC

[67–73]. Notable research studies have also been conducted to develop and improve upon the

commonly used benchmark for electrode material development (i.e., BSCF) in O-SOFCs [32].

Whilst exerting efforts to achieve a SOFC with high performance, stability, and durability that can

operate at intermediate and low temperatures, it is prudent to consider an even more promising

alternative. In 1981, Iwahara et al. [74] pioneered the investigation and demonstration of the

concept of proton conductivity in perovskite oxide-based materials using SrCeO3 material as

electrolyte. This research opened the floodgate of an investigation into the propensity of the

viability of proton-conducting electrolyte materials. It was discovered that proton-conducting

SOFCs also known as protonic ceramic fuel cells (PCFCs) are more promising in achieving high

5
performance at an intermediate to low temperature [75,76]. Compared to O-SOFCs, there are less

reported articles on PCFCs development because it is relatively at the early stage. Over the past

years, PCFCs have gradually garnered attention partly because of the certain unique merits they

possess such as lower activation energy for proton conduction and potentially lower operation

temperature capability. The comparison between O-SOFCs and PCFCs is discussed in detail in

Section 1.2.

1.2 Comparison between O-SOFC and PCFC

Figure 1 illustrates the schematic of O-SOFC and PCFC. The most distinctive feature which

differentiates P-SOFC from O-SOFC is the mode of operation of the electrolyte. The electrolyte

of PCFC conducts protons while that of O-SOFC conducts oxygen ions during operation.

O-SOFCs is characterized by the migration of oxygen ions from the cathode side to the anode side

through the electrolyte membrane when the air supplied to the cathode is reduced after reacting

with the electrons received from the anode via the externally connected circuit.

In contrast to the traditional oxygen ion-conducting SOFC where oxygen ions migrate from the

cathode to the anode, the protonic ceramic fuel cells (PCFC) are SOFCs in which the migration

species are predominantly protons, which migrate from the anode to the cathode at relatively lower

activation energy with the formation of water at the cathode side as illustrated in Figure 1. The

lower activation energy for the migration of protons through the electrolyte and the formation of

water at the cathode is advantageous [77,78]. They give PCFCs an edge over the oxygen ion-

conducting SOFC because there will be no problem of fuel dilution at the anode since the water

formation will only occur at the cathode. Thus, the unreacted hydrogen fuel can be directly

recycled for reuse. In addition, the maximum theoretical efficiency of PCFCs is higher than that

6
of O-SOFC since this theoretical efficiency increases with decreasing temperature. PCFCs are also

compatible with multiple fuel types and when hydrocarbon fuel such as methane is used, there can

be simultaneous production of electricity and useful byproduct such as ethylene (which helps in

the regulation of physiological processes particularly in plant growth) [28,79]. Another interesting

benefit of the formation of water at the cathode side is that there will be an easier CO2 capture and

sequestration since the water formed will be separated from CO2.

Figure 1: Illustration showing the working principle of solid oxide fuel cells with hydrogen and

air being fed to the cell via the anode and cathode, respectively. (a) oxygen ion-conducting SOFC

(O-SOFC) and (b) protonic ceramic fuel cell (PCFCs)

Furthermore, several studies have suggested that P-SOFCs have the potential of resisting the

poisoning effect of H2S [80]. However, despite the numerous potentials of PCFC in achieving a

state-of-the-art energy conversion technology, there are still certain challenges, particularly with

7
the anodic and cathodic reaction processes, that need to be thoroughly investigated. For instance,

there are still issues related to the sintering, conductivity, stability, and durability of PCFC

electrolyte materials which are detrimental to the development and commercialization of ceramic

fuel cells.

2.0 Fundamental Background

2.1 Extraction of relevant articles related to PCFCs from Scopus database

After the perusal of notable review articles as well as other classical research works in PCFCs such

as those of Kreuer [81], Duan et al. [82], Fabbri [83], among others [84,85], the search string for

the extraction of all related articles to PCFC development was formulated as follows: (TITLE-

ABS-KEY("protonic SOFC*" OR "proton-conducting solid oxide fuel cell*" OR "proton ceramic

fuel cell*" OR "proton-conducting ceramic fuel cell*" OR "ceramic fuel cell*" OR "protonic

ceramic fuel cell*" OR "solid oxide fuel cell*") AND TITLE-ABS-KEY("proton-conducting*" OR

"proton conductive*" OR PCFC OR H-SOFC OR P-SOFC)) AND ( LIMIT-TO ( DOCTYPE," ar"

) OR LIMIT-TO ( DOCTYPE, "re" ) ) AND ( LIMIT-TO ( LANGUAGE, "English" ) ). After the

use of this search string in the retrieval of all articles relevant to the subject of interest from Scopus

database, manual exercise was carried out to pick the top articles using criteria such as number of

citations, relevance of the article abstracts, among others. The articles retrieved were also fine-

tuned as illustrated in the search string to be restricted to journal articles and reviews. Based on

the outcome of the results from this search the publication trend for PCFC related research is

summarily illustrated in Figure 2.

8
 120

100
Number of SCI Publications

80

60

40

20

Year

Figure 2: Annual publication trend of PCFC related research from inception till date (2021).

Based on the annual research output in this area, as shown in Figure 2, it is evident that there has

been a continuous and significant increase in efforts exerted towards the development of protonic

ceramic fuel cells which subsequently signals the relevance of this research area.

2.2 Proton conduction mechanisms in PCFC materials

2.2.1 Protonic defects

Proton uptake within the structure of ceramic oxide materials is predominantly due to their oxygen

deficient nature induced by either extrinsic or intrinsic defects. The latter are defects attributed to

alterations in the material structure (such as the absence of an atom) while the former are defects

9
due to impurities or substitution of the B-site species with acceptor dopants as illustrated in

equation (1)[81].

Acc2 O3 + 2BB× + 0.5O2 → 2AccB′ + Vӧ + 2BO2 (1)

where Acc stands for the acceptor dopants which is a trivalent cation and B symbolizes the host

specie at the B-site.

The above mechanism is the predominantly observed mechanism for proton defect formation in

proton conducting solid oxide electrolysis and fuel cells. However, proton defect can also be

formed through another means which involves a non-oxygen defect participating proton

incorporation in the presence of hydrogen enriched atmosphere as shown in equation 2.

H2 + 2O×
O → 2OHȯ + 2e
′
(2)

Nevertheless, this latter category of materials is not suitable and used as electrolyte materials

because of the formation of electronic defects as compensational charges which eventually triggers

electronic conductivity [86].

Hence, in a sodden atmosphere, protonic defects are formed through the dissociation of water into

two hydroxyl ions in the presence of oxygen lattice and oxide ion vacancies as illustrated in

equation 3. The formation of these hydroxyl ions is due to the covalent bond formation between

the lattice oxygen from the structure and a proton, and also as a result of the filling of the oxygen

ion vacancy by the other hydroxide ion to form a protonic defect [81].

H2 O + O×
O + Vӧ ⇋ 2OHȯ (3)

10
where 𝑂𝑂× symbolizes the lattice oxygen, 𝑉ӧ symbolizes the oxygen vacancy and 𝑂𝐻ȯ represents

the proton defect.

Based on Equation 3 which is known as hydration equation, proton uptake involves acid-base

reaction involving the dissociative incorporation of water into oxide ion vacancies and it implies

that an increase in the partial pressure of water will consequently result in the increase of proton

uptake and a decrease in oxygen vacancy concentration. The hydration process can be represented

by the law of mass action as shown in equation 4.

[OHȯ]2
𝐾ℎ𝑦𝑑𝑟𝑎𝑡𝑖𝑜𝑛 = ×] (4)
𝑝𝐻2 𝑂 [𝑉ӧ][𝑂𝑂

2.2.2 Proton transport mechanism

For decades, the concept of proton transport mechanism in ceramic oxide materials has been long

debated and researched. Of all the various mechanisms proposed, the Grotthuss mechanism

appears to be the most adopted mechanism. According to this mechanism, the migration of proton

is by hopping which is caused by a thermally activated process in the form of rapid rotation and

reorientation of proton, and the diffusion of the proton from one neighboring oxygen ion site to

the other as illustrated in Figure 3. This conception is authenticated by measurements of perovskite

oxide H/D isotope-effect as shown in

11
Figure 3: Proton transport mechanism in a typical ABO3 perovskite oxide material [87]. Copyright

2016, Royal Society of Chemistry.

2.3 Overview of P-SOFC component materials

Just like solid oxide fuel cells, the major components of a protonic ceramic fuel cell are the dense

electrolyte, the cathode, and the anode. However, the electrolytes of P-SOFCs conduct protons

instead of just oxygen ions as in the case of the traditional O-SOFCs. The electrolyte material must

allow easy and swift migration of protons from the anode to the cathode with a very minimal ohmic

resistance. For this to occur, the electrolyte material must be dense to ensure maximum

conductivity of protons through the electrolyte and minimize reactant crossovers [88]. It is also

essential that the electrolyte material possess good chemical and thermo-mechanical compatibility

with the other cell components and the atmospheric environment to ensure reasonable stability and

durability. Section 3.0 presents more details about the electrolytes used in P-SOFCs.

On the other hand, the cathode electrode should have excellent diffusion paths and ionic

conductivity (i.e., especially for protons) to extend the cathode reaction zone throughout the

electrode surfaces. The cathode should also possess good electronic and ionic conductivity to

reduce polarization resistance. Likewise, it should possess excellent catalytic activity towards

ORR since cathode reactions in proton-conducting solid oxide fuel cells start with oxygen

12
adsorptive dissociation on the catalyst's surface. The other qualities a good cathode material for P-

SOFC should possess are good compatibility with the electrolyte, excellent chemical, and physical

stability, and sufficient porosity to provide sufficient transport paths for oxygen and stream

molecules. Comprehensive detail of the cathode requirements and other insightful information can

be found in Section 3.2.

The anode material should possess sufficient porosity (about 20 – 40%) and have a satisfactory

conductivity [89]. It is also desirable that the anode material maintains excellent compatibility with

multiple fuels such as hydrogen, natural gas, methanol, ethanol, and other hydrocarbons

[28,90,91]. It should possess a good surface area with reasonable electrical conductivity and

chemical compatibility with adjoining components under reducing conditions at the operating

temperature. The anode material should also have a compatible TEC with other cell components

as well as sufficient mechanical strength to support the cell, in the case of anode-supported cells

[92]. See Section 3.3 for more details about the anode materials for P-SOFCs.

The early P-SOFCs were high-temperature proton-conducting SOFCs. They were often referred

to as high-temperature proton conductors (HTPCs) to differentiate them from polymer electrolyte

membrane fuel cells (PEMFCs) that operate at low temperatures (< 100 degrees Celsius).

However, attention is currently shifted to intermediate and low temperature operating P-SOFCs.

This is because it is cheaper and can potentially increase the durability of SOFC cell components

thereby hastening the commercialization process. Attempts have been made to develop

intermediate to low temperature operating oxygen ion-conducting solid oxide fuel cells, but this

has been challenging. Another viable alternative that has drawn much attention lately is the proton-

conducting solid oxide fuel cells. It is quite advantageous to O-SOFC on many fronts. It has lower

activation energy and has been reported to be coking and sulfur resistant in reputable studies.

13
Despite the benefits of P-SOFCs, research is still ongoing to improve their performance, stability,

and durability.

2.4 Naming conventions for PCFC materials

Duan et al. [91] proposed a naming convention for the various material’s stoichiometric

compositions to facilitate uniformity and understanding among various researchers focused on P-

SOFC research. If the compound is in the form of BaCe1−x Yx O3−δ and BaZr1−x Yx O3−δ , it should

be represented with BCYX and BZYX, respectively and the value of X should be 𝑥 × 100. For

instance, the abbreviation for BaCe0.8 Y0.2 O3−δ will be BCY20 and that of BaZr0.8 Y0.2 O3−δ will be

BZY20. For other categories of compounds in form of BaZr1−x−y Cey Yx O3−δ , the format of the

abbreviation will indicate the B-site major constituent. If y < 1– x – y, then Zr will be the major

B-site constituent and the short form will be BZCYTY, where T = (1 – x – y) × 100. However, if

y > 1 – x – y, then Ce will be the major B-site constituent, and the abbreviation will be in the form

BCZYYT, where Y = y × 100 and T = (1 – x – y) × 100. For instance, the abbreviations for

BaCe0.6 Zr0.2 Y0.2 O3−δ and BaZr0.6 Ce0.2 Y0.2 O3−δ will be BCZY62 and BZCY62, respectively.

Finally, if the compound happens to be in the form of BaZr1−x−y−z Cey Yx Ybz O3−δ , it will follow

the same rule as in BaZr1−x−y Cey Yx O3−δ compounds earlier described with only an exception that

all the percentage constituent of all the B-site compositions will reflect. For instance, the

abbreviation of the compounds BaZr0.4 Ce0.4 Y0.1 Yb0.1 O3−δ and BaZr0.7 Ce0.1 Y0.1 Yb0.1 O3−δ will be

BZCYY4411 and BZCYYb7111, respectively.

14
 3.0 Materials development for various components of PCFCs

3.1 Electrolyte materials

Decades of research have revealed that the best protonic ceramic oxide materials are ABO 3

structured perovskite oxides in which the A-sites are predominantly filled with alkaline earth

metals or rare metals with relatively large ionic sizes such as Ca, Sr, Ba and La while the B-sites

are dominated by smaller sized tetravalent elements such as Zr and Ce [93,94,94–96]. These

materials are relatively stable and exhibit a high level of proton conductivity. Ba for instance, has

a large ionic size and for this reason, it is an A-site dominant material whereas Ce and Zr are B-

site dominant cations, respectively. When B-sites of these proton conducting materials are doped

with extrinsic trivalent elements (i.e., impurities) such as Yb, Y, Gd, In, among others, they will

create oxygen vacancies in the material which will in turn enhance the proton conductivity of the

material.

Figure 4: ABO3 structure of a typical protonic ceramic electrolyte material.

15
Figure 4 illustrates the unit cell ABO3 structure of a typical proton conducting perovskite oxide

electrolyte material. Section Proton conduction mechanisms in PCFC materialsdiscusses the

mechanisms of proton conduction and transport in proton conducting ceramic materials.

A summary of the electrochemical performances of P-SOFC single cells with proton conducting

electrolyte materials is presented in Table 2.

3.1.1 Proton Conductivity and Stability of ceramic oxide electrolyte materials

3.1.1.1 Barium cerate-based materials

BaCeO3 based oxides are one of the most explored perovskite oxide materials for proton-

conducting electrochemical systems [84,97–103]. These materials exhibit mixed conductivity (i.e.,

ionic, and protonic) and they find application in various systems such as steam electrolyzers for

hydrogen production, and electrolytes for proton-conducting solid oxide fuel cells. The proton

conductivity in this category of protonic electrolyte materials stems from the interaction between

oxygen vacancies and water vapor as described in [85]. Furthermore, an early investigation of

proton conductivities of various perovskite oxide-based materials such as indates, hafnates,

scandates, yttrates, tantalates, zirconates of alkali-earth elements, and barium cerates, confirms

that those based on barium cerates have the highest conductivities [81,104]. The higher proton

conductivity in BaCeO3 based oxides (i.e., 10-2 S cm-1 at 600 oC [105] ) could be due to their

relatively low electronegativities, larger ionic radii due to the Ba cation in their A-sites, or/and

their lower grain-boundary resistance on the overall resistance of the perovskite oxide material

[97]. Also, studies have confirmed that Sr/CaCeO3 and Sr/CaZrO3 based oxides have poor

16
hydration capability and lower proton conductivity compared to BaCeO3 based oxides as shown

in Figure 5.

Figure 5: Proton conductivities of BaCeO3 electrolyte material relative to other protonic ceramic
materials [81].

However, later studies suggested that the high proton conductivity in BaCeO3 based oxides should

not be the major yardstick in concluding the viability of their application in electrochemical

systems due to their low stability in water and other acidic compounds [85,102,106]. Also, Bhide

et al. [107] confirmed that BaCeO3 based electrolyte materials have poor stability relative to other

electrolyte materials as shown in Figure 6. BaCeO3 based materials have reaction affinity for

atmospheric gases (such as illustrated in equations 5-8) and this causes the cerate phase to be

decomposed. Equations 5 – 8 show what happens when BaCeO3 reacts with water or any acidic

compound.

17
 𝐵𝑎𝐶𝑒𝑂3 + 𝐻2 𝑂 → 𝐵𝑎(𝑂𝐻)2 + 𝐶𝑒𝑂2 (5)

𝐵𝑎𝐶𝑒𝑂3 + 𝐶𝑂2 → 𝐵𝑎𝐶𝑂3 + 𝐶𝑒𝑂2 (6)

𝐵𝑎𝐶𝑒𝑂3 + 𝑆𝑂2 → 𝐵𝑎𝑆𝑂3 + 𝐶𝑒𝑂2 (7)

𝐵𝑎𝐶𝑒𝑂3 + 𝐻2 𝑂 → 𝐵𝑎𝑆 + 𝐻2 𝑂 + 𝐶𝑒𝑂2 (8)

Due to the challenges encountered with the use of BaCeO3 based oxides as electrolyte materials

for proton-conducting solid oxide fuel cells, efforts were channeled toward developing materials

with excellent mixed conductivity and satisfactory stability against water and acidic

atmospheres[81,87,94,108–114]. Some of those strategies employed were (i) co-doping of

BaCeO3 using various suitable elements which could either be metallic or non-metallic, (ii)

introduction of phases with high stability properties to the BaCeO3 based material in the form of

composite material development. Based on the outcome of various research works, zirconium was

found to be the most suitable element to improve the stability of BaCeO3 [99], although at the

expense of other electrical properties of the material as will be discussed in the next section.

18
Figure 6: Stability of various proton conducting electrolyte materials based on different pCO2 and
temperatures reproduced from [115]. Copyright Elsevier, 2008.

3.1.1.2 Barium zirconate-based electrolyte materials

It has been established that the cerate-based perovskite oxide materials exhibit the highest protonic

conductivity among all other perovskite oxide materials, with BaCeO3 based oxides being the

category of cerates with the highest conductivity. Nevertheless, they are very unstable under

practical conditions in electrochemical systems. The Zirconium-based oxides on the other hand

are reputable for their high stability under various acidic and atmospheric conditions. BaZrO3

based oxides are chemically stable in water and CO2 environments. Lu et al. [115] established the

relationship between increasing partial pressure of CO2, Zr content, x and equilibrium reaction

temperature of BaCe1-xZrxO3. They confirmed that the stability of BaCe1-xZrxO3 increases with

increasing Zr content, x at a given CO2 partial pressure as illustrated in Figure 7.

19
Furthermore, BaCeO3 and BaZrO3 based oxides have ionic conductivities in the range of 10-2 and

10-1 S cm-1 at low and intermediate temperatures[116,117]. However, certain challenges limit their

application as electrolyte materials in proton-conducting solid fuel cells. BaZrO3 based oxides have

issues of significant grain boundary resistance and poor sintering.

Figure 7: Effect of Zr content and partial pressure of CO2 on equilibrium reaction temperature of

BaCe1-xZrxO3, reproduced from [115]. Copyright 2008, Elsevier.

3.1.2 Grain boundary characteristics of PCFC electrolyte materials

One of significant influencing factors affecting the conductivities of proton conducting solid oxide

fuel cells is their grain boundary characteristics[118–121]. Grain boundary resistance has been

identified to be a problem, particularly to the conductivity of BaZrO3 based oxides. Hence, as a

rule of thumb, as the grain size increases, the material conductivity increases and vice versa.

BaZrO3 based oxides on the other hand are characterized by small sized grains at the grain

boundaries which is responsible for their high grain boundary resistances and low conductivity

[122]. Grain boundary architecture is often influenced by segregation forces causing acceptor

20
dopants to accumulate around materials grain boundary core as well as depleting oxygen vacancies

and protons. The consequence of this interaction is the formation of space effects that influence

the transport of ions as shown in Figure 8.

Figure 8: Space charge layer model at the grain boundary core of a typical PCFC electrolyte
material. Copyright 2013, Elsevier.

Iguchi et al. [123] investigated the effects of grain boundary diameter and microstructure on the

electrical conductivities of BaZrO3 based oxides. They particularly considered Y-doped BaZrO3

prepared by solid state reaction process and Pechini method subjected to different sintering

conditions. It was confirmed that the electrical conductivity of the material was significantly

affected by the duration of sintering with the sample subjected to 200 h sintering time exhibited

the lowest electrical conductivity. However, the sample preparation methods had no effect on the

grain boundary characteristics [123]. Y-doped BaZrO3 with 20% doping level have been widely

used and considered to be excellent candidates for PCFC electrolytes. However, the percentage

level of doping of BaZrO3 with Y (i.e., BZY20) often leads to the formation of secondary phase

(i.e., BaY2NiO5) thereby compromising the BZY20 as shown in Figure 9. This implies that the

subsequent co-sintering of the supposed BZY20 with NiO will no longer be a 2-phase equilibrium

comprising just BZY20 and NiO. Hence, it is proposed that this problem can be solved by limiting

21
the doping level of Y in BZY20 to a maximum of 12% or introducing other dopants such as Yb

[124]. The phenomenon described involving foreign phase formations significantly affects the

transport of ions around the grain boundaries [125].

Figure 9: Expected secondary phases to be formed when various BZY compositions are co-
sintered with NiO [124]. Copyright 2019, Royal Society of Chemistry.

3.1.3 Sintering of PCFC electrolyte materials

As earlier discussed in the previous section concerning grain boundary resistant problem of

BaZrO3 based oxide, various approaches have been employed to address this challenge. The use

of several sintering aids such as NiO, ZnO, CuO, etc., have been proposed [126–128]. However,

Han et al. [112] and others suggested that the use of sintering aids such as NiO, ZnO, and CuO

impedes the proton conductivity in BZY20 and leads to the creation of hole conduction in an

oxidizing atmosphere [127,129,130]. The most investigated doped BaZrO3 oxide is yttrium doped

barium zirconate, BZY. There have been co-doping strategies of yttrium barium zirconates with

other elements such as Nd, In, Sn, Pr, and Yb to improve the sintering and proton-conducting

22
properties of barium zirconates which has led to certain promising outcomes [131,132]. Asides

from the introduction of sintering aids to barium zirconates and co-doping strategies, the use of

PLD has also been used to improve the sintering of barium zirconates by Pergolesi et al.[133].

However, PLD is an expensive method and not suitable for large-scale applications. Due to the

various challenges enumerated, an alternative approach to getting a superior proton-conducting

electrolyte for P-SOFCs will be a natural combination of yttrium doped barium cerate and yttrium

doped barium zirconate to get cerium and yttrium doped barium zirconates as will be explored in

the subsequent section.

3.1.4 Other Materials and Challenges

The combination of BCY and BZY has been identified to be a promising approach to getting an

improved proton-conducting electrolyte for P-SOFCs. Katahira et al. [99] investigated the effects

of variations in the constituents of BCZY. They observed that increasing the Zr content increases

the stability of the compound against CO2 but sacrifices conductivity. Likewise, they varied the

Ce content and confirmed that its presence increases the conductivity and sinterability of BCZY.

Overall, they concluded that BCZY is stable with an acceptable conductivity. For instance, Zuo et

al. [134] investigated the conductivity and stability of BCZY712 at a low temperature of 500 oC.

It was discovered that BCZY712 exhibited excellent ionic conductivity of 0.009 S cm-1 which

surpassed that of LSGM, GDC, and YSZ. Likewise, in terms of stability, the structure of BCZY712

was confirmed to be the same before and after exposure to CO2, H2O, and CO2 and H2O. Another

innovative product of the combination of BCY and BZY is BCZY442 [135]. This electrolyte

material was reported to have a high bulk proton conductivity and an excellent tolerance to CO2.

However, the challenge with is material lies in its high sintering temperature and low grain

boundary proton conductivity [136]. Other approaches that have been employed by researchers are

23
the introduction of several dopants to the B-sites of BCY and BZY. An example of a breakthrough

with this approach is the development of BCZYYb7111 in 2009 by Yang et al [137]. The

introduction of Yb into BCZY improved the conductivity and stability of BCZY against sulfide

and other hydrocarbons. Later studies revealed that CO2 affects the stability of BCZYYb7111. The

exceptional discovery of another stoichiometric manipulation of BCZY by Choi et al. [138] gave

rise to BCZYYb4411. This material was reported to have a high tolerance for CO2, and this was

attributed to the higher content of Zr. Also, the material has relatively improved performance with

high resistance to coking and sulfur atmospheres.

Table 2: Selected electrochemical performances of single cells with P-SOFC electrolyte

materials operated under humidified hydrogen and ambient air.
Electrolyte Power density OCV Temp. Cell configuration (cathode | electrolyte | anode) Ref.
(mW cm-2) (V) (℃)
BaCe0.9Y0.1O3-δ 96 1.145 600 PR2NiO4 | BCY10(85µm) | Ni + BCY10 [139]
BaCe0.9Y0.1O3-δ 150 0.98 600 LSCF8282- BCYb10 | BCY10(13.4µm) | Ni + [140]
BCY10
BaZr0.8Y0.2O3- δ 169 0.97 600 PBC- BZYP | BZY20(20µm) | Ni + BZY20 [141]
BaZr0.8Y0.2O3- δ 110 0.99 600 LSCF6428- BCYb10| BZY20(4µm) | Ni + BZY20 [142]
BaZr0.3Ce0.55Y0.15O3- δ 1302 1.056 600 BSCF| BZCY3(5µm) | Ni + BZCY3 [143]
BaZr0.1Ce0.7Y0.1Yb0.1O3- δ 690 1.04 600 NBSCF| BZCYYb1711(14.7µm) | Ni + [137]
BZCYYb1711
BaZr0.4Ce0.4Y0.1Yb0.1O3- δ 1098 1.01 600 PBSCF| BZCYYb441(15µm) | Ni + BZCYYb441 [138]
BaZr0.1Ce0.7Y0.2O3- δ 428 1.01 600 SFNb | BZCY172 (20µm) | Ni + BZCY172 [144]
BaZr0.1Ce0.7Y0.1Yb0.1O3- δ 580 0.95 600 LSM-SDC | BZCYYb1711(12µm) | Ni + [145]
BZCYYb1711
BaZr0.1Ce0.7Y0.1Yb0.1O3- δ 700 0.98 600 LSCF6428-SDC | BZCYYb1711(12µm) | Ni + [146]
BZCYYb1711

For cathode.
LSCF8282- BCYb10 = La0.8Sr0.2Co0.8Fe0.2O3- δ - BaCe0.9Yb0.1O3- δ; PBC- BZYP = PrBaCo2O5+δ- BaZr0.7Y0.2Pr0.1O3- δ ; LSCF6428 - BCYb10 =
La0.6Sr0.4Co0.2Fe0.8O3-δ - BaCe0.9Yb0.1O3- δ; BSCF = Ba0.5Sr0.5Co0.8Fe0.2O3-δ; NBSCF = NdBa0.5Sr0.5Co1.5Fe0.5O5+δ ; PBSCF =
PrBa0.5Sr0.5Co1.5Fe0.5O5+δ; SFNb = SrFe0.95Nb0.05O3- δ; LSM-SDC = La0.75Sr0.25MnO3- δ - Ce0.8Sm0.2O2- δ; LSCF6428-SDC = La0.6Sr0.4Co0.2Fe0.8O3- δ -
Ce0.8Sm0.2O2- δ

3.2 Cathode Materials development for PCFCs

The cathode is the most explored research area in ceramic fuel cell development because of the

high activation loss for ORR at the cathode during low and intermediate temperature operating

conditions. Thus, developing highly active and stable cathode materials could contribute

24
significantly to the performance improvement of PCFCs. Unlike the case of oxygen ion conducting

solid oxide fuel cells where the cathode reaction involves oxygen adsorptive dissociation on the

catalyst surface followed by the diffusion of oxygen ions to the anode through the electrolyte, in

PCFCs, the oxygen adsorptive dissociation first occurs on the catalyst surface, after which the

oxygen ions react with the protons that migrated from the anode through the electrolyte to form

water. Equations 9 and 10 illustrate the adsorptive dissociation reactions in O-SOFC and PCFCs,

respectively. Detailed stepwise elementary reactions at the cathode for P-SOFCs are presented in

Table 3 while the reaction pathway for a single-phase proton, electron, and oxygen ion-conducting

cathode material for proton-conducting solid oxide fuel cells is illustrated in Figure 10.

𝑂2 + 4𝑒 − → 2𝑂2− (9)

𝑂2 + 4𝑒 − + 4𝐻 + → 2𝐻2 𝑂 (10)

Figure 10: Schematic illustrating reactions in a single-phase triple conducting P-SOFC cathode.

25
The transfer mode in PCFC cathodes can be divided into four categories; the electron-conducting

single-phase cathodes, the proton and oxygen ion-conducting cathodes (i.e., either single-phase or

composite material), the oxygen and electron-conducting (MIEC) cathodes (i.e., as a single-phase

or composite material) and the proton-electron-oxygen ion-conducting single-phase cathodes (i.e.,

as shown in Figure 10. A schematic illustration of the different transfer modes of cathode materials

in P-SOFC is presented in Figure 11.

Figure 11: Cathodic reactions in PCFCs [147] for (a) Single-phase electron-conducting cathode
materials, (b) proton and oxygen ion-conducting cathode materials, (c) MIEC cathode materials,
and (d) proton, electron, and oxygen ion-conducting cathode materials. Copyright 2018, Royal
Society of Chemistry.

26
The foundational concepts for the development of cathode materials for proton-conducting solid

oxide fuel cells stem from the knowledge of cathode development for oxygen ion-conducting solid

oxide fuel cells. In the conventional SOFCs, what is currently prominent is the development of

single-phase mixed ionic and electronic conducting (MIEC) cathodes which are different from the

early traditional SOFCs where cathode reactions are limited to the triple-phase boundary (i.e., the

interface where oxygen ion, electrolyte, and cathode coincide)[28,148]. The MIEC concept in

SOFCs gives the possibility of extending the reaction zone beyond the TPB to the whole surface

of the cathode depending on the efficacy of the cathode constitutive elements [25,149]. Some of

the most outstanding results of cathode materials developed for SOFC with MIEC are

Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF)[150] and La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF)[151]. Besides these

materials developed, other categories of materials developed in later years are double perovskites

(i.e., AÁB2 O5+δ based oxides such as PrBaCo2 O5+δ [152]), Ruddlesden-Popper (i.e.,

An+1 Bn O3n+1 based oxides such as La2 NiO4+δ [153]) phases and layered ferrites [154] (e.g.,

Sr2Fe2O5). Other procedures developed to improve oxygen exchange rate by controlling the

cathode morphology include in situ exsolution[110], impregnation[155,156], and atomic layer

deposition[44].

P-SOFCs and PCFCs share certain common requirements in cathode development, such as

consideration of cost of constituent cathode materials, compatibility with other cell components,

stability, durability, and performance. Some other requirements such as proton conductivity,

among others are peculiar to PCFCs.

3.2.1 Activity

For PCFCs, it is essential that the cathode material possesses effective proton diffusion paths to

extend the reaction zone to a higher specific area of active sites which implies that a PCFC cathode
27
material should have a high catalytic activity towards oxygen reduction reaction (ORR) [157]. The

cathode catalyst should be capable of effectively dissociating the adsorbed oxygen on its surface

for further reactions at the cathode. One of the strategies for increasing the catalytic activity of

PCFC cathode material is therefore substituting the A-sites with lower valence ions which have

proven to increase electronic conductivity and oxygen adsorptive dissociation. Hence, proton

conductivity in PCFCs can be achieved by either introducing proton conductivity into an existing

conventional MIEC cathode as in the case of BaCe0.8Sm0.2O2.9 being introduced into

Sm0.5Sr0.5CoO3 to achieve a proton-conducting composite cathode with a highly reduced

polarization resistance[158]. Another way of achieving a highly active proton-conducting cathode

material is by designing single-phase oxides with a triple conducting capability (i.e., proton,

oxygen ion, and electron conductivity) as illustrated in Figure 11 (d) and Figure 10. This oxide

should at least have a conductivity of 1 S/cm to ensure excellent performance. In this case, the

reaction is extended to the entire surface of the cathode which in turn improves the catalytic activity

of the cathode. The stepwise reaction paths for these novel P-SOFC cathodes with triple

conductivity are summarily described in Table 3.

Table 3: Basic steps and order of reactions at the cathode for a typical P-SOFC.
Step Reaction(s) Description

1 O2 (g) → O2(ad) Molecular oxygen adsorption

2 O2(ad) → 2O(ad) Molecular oxygen dissociation of adsorped oxygen

from the air

3 O(ad) + e− → O−
(ad) ; Oxygen reduction at the cathode

O(ad) + 2e− → 2O2−

(ad)

4 O(ad) → OTPB Surface diffusion at the electrode/electrolyte/oxygen

O− −
(ad) → OTPB
ion boundary

28
 5 O− −
bulk → OTPB Bulk diffusion of oxygen throughout the cathode

+ +
6 2Hbulk → 2HTPB Proton migration towards the anode

+
7 2HTPB + O2− −
TPB → OHTPB Formation of water at the triple-phase boundary

− +
OHTPB + HTPB → H2 OTPB

8 H2 OTPB → H2 O(g) Evaporation of water

Kim et al. [159] developed a single-phase cathode material with triple conductivity,

NdBa0.5Sr0.5Co1.5Fe0.5O5+δ (NBSCF). A low polarization resistance of 0.081 Ωcm2 was achieved

at a temperature of 700 oC [159]. Also, proton-conducting cathode materials can be derived from

proton-conducting electrolytes such as BaZrO3 and BaCeO3 based electrolytes. The electronic

conductivity and catalytic properties of the proposed cathode materials can be improved by doping

the B sites of proton-conducting electrolytes with highly catalytic elements such as Co and Fe as

in the case of BaZr1-xCoxO3−δ [160] and BaZr1-xFexO3−δ . In 2015, Duan et al. [82] developed the

novel cathode material, BaCo0.4Fe0.4Zr0.1Y0.1O3−δ (BCFZY0.1). This cathode material was

reported to have an excellent ORR at low and intermediate temperatures. When hydrogen fuel was

used, the peak power density (PPD) was 455 mW cm-2 at a low temperature of 500 oC and when

methane fuel was used, the PPD was 142 mW cm-2 at the same temperature. In 2021, Liang et al.

[161] doped the high performance BCFZY cathode material with 5% Ni. This dopant interestingly

improved the ASR and PPD of BCFZY material in both P-SOFC and PCFC as illustrated in Figure

12. Another interesting strategy for achieving a high activity in PCFC cathode materials is through

the design of self-assembled nanocomposite cathode materials. Self-assembly design of cathode

materials is a novel and emerging approach for preparing composite cathode materials with

desirable qualities ranging from high activity to excellent thermo-mechanical compatibility with

other cell components. This strategy has earlier been used in the preparation of cathode materials

29
with excellent MIEC in O-SOFCs. For instance, Qi et al. [162] employed the strategy of self-

assembly cathode design to prepare cubic-hexagonal perovskite nanocomposites (i.e.,

BaCo0.6Zr0.4O3−δ (BZC-BC) nanocomposite comprising cubic BaZr0.82Co0.18O3−δ (BZC) and 12H

hexagonal perovskite material, BaCo0.96Zr0.04O2.6−δ (12H-BC)) for O-SOFC. The material

exhibited an excellent compatibility (i.e., TEC) with GDC electrolyte also a high PPD of 1094

mW cm-2 at 650 oC. Recently, Song et al. [163] employed the self-assembly cathode design

approach to prepare a nanocomposite cathode material comprising different phases, proton and

electronic conductor phase, BaCexYyCozO3−δ (P-BCCY), the MIEC phase, BaCoxCeyYzO3−δ (M-

BCCY) and another MIEC phase, BaCoO3−δ (BC). The different inherent phases are entwined to

achieve a highly active triple conducting material with the active sites extended throughout the

cathode material. At 550 oC, a high PPD of 508 mW cm-2 was achieved which was stable for over

800 h. Despite the significant progress that has been made in the development of P-SOFC cathodes,

the electrochemical processes on the cathode need to be further investigated.

Figure 12: The performance of BCFZYN and other classical electrode materials used in both O-
SOFCs and PCFCs, respectively (a) ASR in air with SDC and BZCYYb electrolyte (b) PPD with
Ni + SDC│SDC│cathodes and Ni + BZCYYb│BZCYYb│cathodes[161]. Copyright 2021,
Elsevier.

30
 3.2.2 Conductivity improvement strategies for PCFC cathode materials

Another essential requirement for P-SOFC cathode material is good electronic conductivity. This

is important to achieve a cathode material with low ohmic resistance. The idea of electronic

conduction stems from the formation as well as the transportation of electron holes which are

achieved through the introduction of transition elements (i.e., Ni, Mn, Fe, Co) in the B-site. The

electron holes can be further increased by substituting ions with lower valences as in the case of

Ba2+, Ca2+, and Sr2+ in the A-site[164]. Furthermore, Zohourian et al. [165] and Papac et al. [166]

buttressed on mixed and triple conductivity of cathode materials for P-SOFCs by emphasizing on

proton uptake mechanisms in perovskite oxide materials which has been elaborately discussed in

Section 2.2. To develop and design a high-performance cathode material with superb proton,

electron, and oxygen ion conductivity for PCFCs, certain strategies have been suggested in the

literature[91,109,167]. The materials that are reported to be most suitable for achieving excellent

triple conducting single-phase cathodes are either ABO3−δ perovskites, AÁB2 O5+δ double

perovskites, and An+1 Bn O3n+1 Ruddlesden-Popper with their A and B sites doped with elements

such as Ba, Sr, Zr, Cu, Mn, Co, and Ni[26,77,168–173]. It is best to consider materials with cubic

structures and large lattice volumes because they enhance hydration and proton conduction. It is

also essential when selecting dopants to consider transition metals with multiple oxidation states

because that will significantly enhance redox capability and good electronic conductivity. The B-

site cation should possess higher electronegativity than the A-site cation to promote proton uptake

and lattice hydration as in the case of specific elements such as Zn, Y and Zr [165]. Also, the A-

site cation should have a larger ionic radius to increase the lattice volume, oxygen vacancy

concentration, and mobility. Furthermore, the A-site dopants should be carefully selected because

31
this greatly influences the stability and performance of the material. Table 4 shows a list of recent

articles with new findings related to cathode material development for P-SOFCs.

3.2.3 Compatibility with other cell components

A good PCFC cathode material should possess excellent compatibility with the proton-conducting

electrolytes, including chemical compatibility and compatibility in thermal expansion coefficient

(TEC). The TEC of the cathode material must match reasonably with that of the electrolyte to

prevent large thermal stress during thermal cycling, which causes the delamination of the cathode

from the electrolyte. The TEC of the cathode materials should be reasonably close to those of the

electrolytes, usually in the range of 10-6 K-1. Past research studies have revealed that Co-based

materials usually have good electrocatalytic activity but also significantly higher TECs than those

of Mn-based materials. Hence, reducing the percentage of cobalt in cathode materials by partially

replacing it with transition metals can cause a reduction in the material’s TEC. Recently, a novel

TEC offset approach was proposed by compositing the Co-containing cathode materials with

negative thermal expansion (NTE) materials to reduce the overall TEC [174]. As a result, high-

performance and durable cathode materials were developed. Although the cathode was for O-

SOFC, the same strategy can be applied to H-SOFC as well.

Table 4: Notable cathode materials for proton-conducting solid oxide fuel cells

Cathode Conductivity Rp (𝛀 𝒄𝒎𝟐 ) PPD (mW cm-2) Cell configuration Ref.

(Scm-1)

Ba2YCu3O6+δ 0.48 0.29@650 175 BYC│BZCY│Ni - BZCY [175]

La1.5Ca0.5NiO4+δ 0.053@700℃ 923 LCN│BZCY│Ni - BZCY [176]

Ba0.95La0.05Fe0.8Zn0.2O3−δ 0.08@750℃ 329 BLFZ│BZCYYb│Ni - BZCYYb [177]

32
Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) 0.189@700℃ 356@600℃ BSCF|BZCY721|Ni + [178]

BaZr0.2Ce0.7Y0.1O3−δ (BZCY721)

BSCF 276@600℃ BSCF|BZCY442|Ni + [179]

BaZr0.4Ce0.4Y0.2O3−δ (BZCY442)

BSCF 508@600℃ BSCF|BZCY305515|Ni + [180]

BaZr0.3Ce0.55Y0.15O3−δ

(BZCY305515)

BSCF 0.5@600℃ 380@600℃ BSCF|BCY|Ni + BaCe0.9Y0.1O3−δ [181]

(BCY)

BSCF–Ag 245@600℃ BSCF–Ag|BZCY811|Ni + [182]

BaZr0.1Ce0.8Y0.1O3−δ (BZCY811)

BaCo0.4Fe0.4Zr0.1Y0.1O3−δ 0.2@600℃ 970@500℃ BCFZY|BZCYYb + NiO (1 [120]

wt %)|Ni +

BaZr0.1Ce0.7Y0.1Yb0.1O3−δ

(BZCYYb)

Ba(Co0.4Fe0.4Zr0.1Y0.1 0.607@550℃ 450@550℃ BCFZYN|BZCYYb4411|Ni + [161]

)0.95Ni0.05O3−δ BaZr0.4Ce0.4Y0.1Yb0.1O3−δ

PrBaCo2O5+δ 305@600℃ PBC|BZCY721|Ni + BZCY721 [183]

Ba0.9Co0.7Fe0.2Nb0.1O3−δ 0.046@600℃ 1062@600℃ [184]

BCFNb|BZCY721|Ni + BZCY721

PrBa0.5Sr0.5Co1.5Fe0.5O5+δ 0.056@600℃ 2160@600℃ PBSCF|BZCYYb4411|Ni + [138]

BaZr0.4Ce0.4Y0.1Yb0.1O3−δ

(BZCYYb4411)

BaCo0.7(Ce0.8Y0.2)O3−δ 0.1@600℃ 1150@600℃ BCCY|BZCYYb|Ni + BZCYYb [184]

3.2.4 Chemical and physical stability

Stability is one of the essential yardsticks to assess the quality of a cathode material used in proton-

conducting solid oxide fuel cells. Any material selected to be used as a cathode for P-SOFC must

possess reasonable chemical stability in CO2, humid air, etc. Ba and Sr are common A-site

elements in cubic ABO3 and double perovskites used as cathodes in P-SOFCs because of their

large ionic size and effect on promoting better oxygen pathways. However, these alkaline earth

33
metals are susceptible to reacting with CO2 in acidic gases-containing environments thereby

causing degradation in the performance of the fuel cell. Despite stability being a crucial quality in

PCFC cathodes, its development has drawn less attention compared to the effort exerted on

improving the performance of PCFC cathodes. Several articles have confirmed that using

monovalent ions such as Zr4+, Hf4+, and Yb3+ to dope cathode materials can significantly enhance

the stability and activity of the cathode material. Tsvetkov et al. [185] hypothesized and

investigated if the use of less reducible cations such as Hf4+, Zr4+, Ti4+, Nb5+, and Al3+ can influence

the stability of a model perovskite material, La0.8Sr0.2CoO3 (LSC). The outcome of the study

revealed that these less reducible cations not only improved the stability but also the oxygen

exchange kinetics. Also, another potential aspect that could adversely affect the stability of cathode

electrode material is the TEC mismatch between the cathode material and other cell components

such as the anode and electrolyte. This is a particularly challenging aspect in cathode material

development in both conventional SOFCs and PCFCs. For instance, Figure 13 illustrates a

schematic of various perovskites materials used as either cathode, electrolyte, or anode material

for the conventional SOFCs. It is clear from the schematic that different material categories have

disparate TECs. Hence, stability does not necessarily increase the ORR but rather, it ensures the

durability of the cathode material. For instance, cobalt-based cathodes are found to possess better

ORR and hence better performance, but they exhibit relatively poorer stability compared with

cobalt-free cathode materials.

34
Figure 13: TECs for different SOFC component parts with their various constitutive
compositions[186] highlighted as follows: Zr Y O (YSZ)[175], Ce Gd O (GDC) [187],La Sr Ga Mg O (LSGM)
0.84 0.16 1.92 0.8 0.2 1.9 0.8 0.2 0.8 0.2 3−δ
[188], 48 vol% Ni–GDC (Ni-GDC-48, porous, 75% theoretical density) [189], Y0.9In0.1BaCo3.3Ga0.7O7+δ (YIBCG) [190], YBaCo3ZnO7+δ (YBCZ) [190],
YBaCo3.2Ga0.8O7+δ (YBCG)[190], La0.8Sr0.2MnO3−δ (LSM)[191], La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF)[192], Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF)[193], La0.6Sr0.4CoO3−δ
(LSC)[194], SrCo0.9Sb0.1O3−δ (SCSb)[49], Sr0.5Sm0.5CoO3−δ (SSmC)[195], GdBa0.5Sr0.5Co1.5Fe0.5O5+δ (GBSCF)[196], NdBa0.5Sr0.5Co1.5Fe0.5O5+δ (NBSCF)[196],
PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF)[196], La0.6Sr0.4FeO3−δ (LSF) [197], and Ba0.95La0.05FeO3−δ (BLF) [198].

Figure 14 illustrates a schematic representation of the different TECs for different cathode and

electrolyte materials used in P-SOFCs and Table 5 provides the details of each electrolyte or

cathode compound represented in Figure 14.

Table 5: TECs of different cathode and electrolyte materials for PCFCs

Material Abbrev. TEC (×10-6) K-1 Ref.

Cathode Electrolyte

La0.5(Ba0.75Ca0.25)0.5Co0.8Fe0.2O3-δ LBCCF 21.7 [199]

BaZr0.1Ce0.7Y0.1Yb0.1O3-δ BZCYYb 10.5 [199]

Y0.8Er0.2BaCo3.2Ga0.8O7+ δ YEBCG 8.41 [200]

(Ba0.85Sr0.15)(Zr0.7Ce0.1Y0.2)O2.9 BSZCY151020 ~10 [201]

BaZrO3 BZO 7.13 [101]

BaCeO3 BCO 11.2 [101]

SrZrO3 SZO 9.7 [202]

SrCeO3 SCO 11.1 [202]

35
 BaZr0.80Y0.20O3-d BZY 8.2 [203]

BaZr0.60Ce0.2Y0.2O3-d BZCY 9.1 [203]

BaZr0.1Ce0.7Y0.2O3-d BCZY 10.1 [204]

Zr0.84Y0.16O1.92 YSZ 10.5 [175]

La1.5Ca0.5NiO4+δ LCN 14.6 [176]

Ba0.95La0.05Fe0.8Zn0.2O3−δ BLFZ 20.4 [177]

25

20 Cathode Electrolyte
TEC (× 10-6 K-1)

15

10

0
BSZCY1…
LBCCF
BZCYYB
YEBCG

BZO
BCO
SZO
SCO
BZY
BZCY
BCZY
YSZ
LCN
BLFZ

Figure 14: TECs of cathode and electrolyte materials for PCFCs.

Finally, it is also expected that PCFC cathode materials should have high porosity. Although, this

porosity is not an intrinsic quality but that achieved by processing. The availability of high porosity

will ensure enough transport paths necessary for oxygen and steam molecules diffusion [205].

3.3 Anode materials development for PCFCs

The anode is one of the essential components of a proton-conducting solid oxide fuel cells.

However, it has attracted less attention compared to the electrolyte and cathode materials. The

36
anode electrode material for P-SOFC should have both electronic and proton conductivity to

increase the number of electrochemically active sites and facilitate an efficient hydrogen oxidation

reaction. At the anode, a hydrogen molecule is oxidized to produce two protons and two electrons

as illustrated in Equation 4.7.

H2 → 2H+ + 2e− (3.7)

The design of anode materials for proton-conducting solid oxide fuel cells is like that of oxygen

ion conducting solid oxide fuel cells. The P-SOFC anodes are cermets produced by mixing NiO

with a proton-conducting electrolyte in which the NiO is subsequently reduced to Ni. This

reduction of NiO to Ni consequently leads to the generation of porosity which is necessary for gas

diffusion and continuous electronic pathway. The rule of thumb is that a composite anode material

is formed by combining an electronic conducting phase (i.e., Ni) with a proton-conducting oxide.

Therefore, the proportion of the mixture of the electronic and proton-conducting phases, the

microstructure, and particulate size of the anode material is important to be decided carefully

because they significantly influence the performance of the cell. The triple-phase boundary

increases with an increasing anode surface area which also speeds up the reaction kinetics. This

desirable large surface area can be increased by using powders with small average grain sizes.

More so, it has been demonstrated that improved symmetric cell performance could be achieved

by controlling the anode porosity [206–208].

One of the studies which attempted to gain insights into the reactions at the anode for P-SOFCs

with the aim of developing superior anode materials is the research conducted by Pers et al. [206].

They investigated the effect of temperature and atmosphere on the hydrogen oxidation reaction at

the Ni-BaZr0·1Ce0·7Y0.1Yb0.1O3-δ (BZCYYb) interface using impedance spectroscopy at different

hydrogen partial pressure in the temperature of 350 – 600 ℃. They asserted that the hydrogen

37
dissociation step is the rate-limiting step for the hydrogen oxidation reaction. Consequently, the

polarization resistance of the cermet Ni-BZCYYb was 0.049 Ω cm2 at 600 ℃ when hydrogen fuel

is used.

Also, Essoumhi et al. [209] investigated the microstructure and electrical characteristics of two

cermets (ceramic-metal composite) with different Ni content using BaCe0.9Y0.1O2.95 ceramic

nanopowders. The proportion of Ni in both cermets (i.e., Ni-BCY) is 35 and 45 vol. % which are

both equivalents to 50 and 60 wt% NiO. It was discovered that an increase in Ni content improved

the porosity and electrical properties of the electrodes.

Chevallier et al. [210] presented a novel wet-chemical route approach for preparing Ni–

BaCe0.9Y0.1O3 – δ cermet. This was achieved by dispersing BCY10 nanocrystalline powder in a

nickel nitrate solution followed by sintering at a temperature of 1000 ℃. It was found out that the

resulting cermet was not tolerant to the CO2 atmosphere at a temperature of 700 ℃ due to the

severe degradation encountered. This renders the use of Ni-BCY anode to be restricted to hydrogen

fuel and highly unsuitable for hydrocarbon-based fuels.

Plekhanov et al. [92] investigated suitable and possible anode materials for LaScO3-based proton-

conducting electrolytes. Ni-LSS5 cermet was produced via solid-state and co-precipitation

methods. They then subjected the LSS5 powder to different production and sintering temperatures

in the range of 1400 to 1500 ℃ and observed the microstructural features and phase compositions.

It was discovered that the electrical conductivity and chemical expansion of Ni-LSS was majorly

influenced by its porosity as opposed to the notion of it being influenced by the various methods

of synthesis employed. The porosity and average grain size of the samples were estimated by

scanning electron microscopy (SEM) image analysis. It was discovered that as the sintering

temperature increases, the porosity decreases as shown in Figure 15.

38
Figure 15: Porosity variation of the various specimens with increasing temperature [92].
Copyright 2021, Springer.

Onishi et al. [211] investigated the performance of Ni-BZY20 cermet used with BaZr0.8Y0.2O3-δ

(BZY20) electrolyte. Ni-BZY20 anode symmetrical cells with a NiO content of 20-70 % were

fabricated and tested. They found out that an increase in NiO content made the sintering process

more difficult with cells failing at 80 wt% NiO. Hence, it was recommended that the proportion

of NiO in the proposed cermet should be less than 70 wt% during cell fabrications.

Ni-based anodes have been vastly employed in SOFCs applications due to their suitability and

good performance. However, despite the benefits derived from the use of Ni-based anodes, certain

drawbacks have been identified especially when the cell operates at a temperature range of 500 –

800 ℃. [212]. Some of those drawbacks include agglomeration of Ni thereby causing anode

performance deterioration with time and coke formation when hydrocarbon fuel is used.

Nevertheless, only a few alternatives have been proposed as in several instances where hydrogen-

39
permeable metal membranes have been used as supporting anodic structure for protonic SOFCs

[213,214].

3.3.1 Sintering of PCFC anode materials

Anode-supported cell construction is often employed in most proton-conducting solid oxide fuel

cell fabrications. In this form of cell construction, the anode is made the thickest layer of the cell

to provide mechanical support for the other cell components. The thick anode layer and the thin

electrolyte layer are often co-sintered at a high temperature. The essence of this is to provide the

necessary support for the electrolyte and ensure good sinterability by a way of enhancing the

quality densification and conductivity of the electrolyte layer. Several studies have highlighted the

roles the cermet plays in ensuring quality sintering in P-SOFC electrolytes[36,126,127].

Duan et al. [120] expounded the use of sintering aids such as CuO and NiO to improve the

densification of the various electrolytes investigated which were BaCe0.7Zr0.1Y0.1Yb0.1O3-δ

(BCZYYb), BaZr0.8Y0.2O3-δ (BZY20), and BaCe0.6Zr0.3Y0.1O3-δ (BCZY63). In order of decreasing

stability, we have BZY20 > BCZY63 > BCZYYb. BCZY63 has relatively better sinterability and

lower grain boundary resistance while BCZYYb has the highest reported conductivity for P-

SOFCs. With a single-cell composition of 40 wt % BCZYYb + 60 wt % NiO | BCZYYb +1.0 wt

% NiO | BCZY63 + BCFZY0.1, a peak power density of 0.455 W/cm2 was achieved at a

temperature of 500 ℃ when hydrogen fuel is used.

Furthermore, the sinterability and performance of the anode electrode are also influenced by the

morphology of the electrode. For instance, the effect of the quantity of carbon microspheres pore

former on the porosity, line shrinkage, electrochemical performance, and thermal expansion of

NiO-BCZY71 was investigated. It was discovered that electrode support with 30 wt% pore formers

40
exhibited the best performance because of its excellent porosity and good triple-phase boundary

reactions [215].

4 General synthesis and fabrication of protonic ceramic oxide materials

For years, manufacturing challenges have impeded the development of proton-conducting solid

oxide fuel cells until recently when novel methods of synthesizing and fabricating proton-

conducting solid oxide fuels emerged. Some of those newly emerged methods for the processing

and fabrication of proton-conducting solid oxide fuel cells are solid-state reactive sintering, anode-

assisted densification of the electrolyte, extrusion, and interface modification [91].

The synthesis and fabrication of protonic ceramic oxide materials (PCOM) involve several high-

temperature and energy-demanding procedures. These procedures are requisite to achieving the

desired phases and microstructures as well as other preferable cell component qualities such as

porous electrodes, dense electrolytes, and highly stable and durable cells [205]. In a study, it was

estimated that materials manufacturing cost accounts for about 30 % of the total proton-conducting

solid oxide fuel cell manufacturing cost [125]. Therefore, it is important to devise measures to

significantly ameliorate the total manufacturing cost for proton-conducting solid oxide fuel cells

by finding alternative and economical fabrication approaches.

Some of the prominently identified measures to significantly reduce PCOM fabrication cost are

lowering various material processing temperatures and spotting compositions that do not require

expensive precursors (i.e., salts or rare earth oxides). One of the recommended cost-effective

methods of synthesizing and fabricating PCOM is solid-state reactive sintering (SSRS)[216]. With

this approach, there is a possibility of reducing the arduous and long manufacturing processes from

above 10 steps to just 3 or fewer in addition to the consequently reduced sintering temperatures,

41
time, and energy consumption. What makes the SSRS approach stand out is the fact that it aids the

sintering process through the incorporation of a small portion of sintering aids (i.e., NiO, ZnO,

CuO, etc.) as expounded in previous sections.

In a study, when 4 wt. % ZnO was added to a well-crystallized BZY powder, a homogeneous

distribution of ZnO was produced in the intergranular region. The resulting modified grain

boundary composition enhances electrolyte sintering and improves grain growth and boundary

mobility caused by an increase in Ba vacancy concentration. Nevertheless, grain boundary

conductivity of unmodified BZY is not improved by the introduction of ZnO, rather the grain

boundaries are highly tuned. More so, the bulk conductivity of ZnO-modified BZY is relatively

lower compared to that of the unmodified BZY. This work gave more insight into the propensity

of synthesizing P-SOFCs with lower sintering temperatures and optimized manufacturing

processes [217].

Other studies leveraged the foundational concept of SSRS to incorporate phase formation, grain

growth, and densification in just a single sintering step which consequently simplified the synthesis

and lowered the fabrication cost of P-SOFCs [82,217,218]. Asides from NiO, other sintering aids

such as Al2O3, LiF, and SnO2 were investigated to see the one which significantly reduces sintering

temperatures. It was found out that NiO is the most effective sintering aid as it reduces the sintering

temperature of BZY20 from above 1600 ℃ to 1400 ℃ with a positive densification rating above

95 %[111]. Furthermore, Tong et al. [125]employed a cost-effective SSRS approach to synthesize

a high-quality Ni-BZY electrode. A record-breaking conductivity of 0.033 S/cm was achieved at

a temperature of 600 ℃ under a wet argon atmosphere. NiO is the most established and widely

used sintering aid in the reduction of sintering temperatures for P-SOFCs[28,125–128,219].

42
Asides from sintering aids, the other factor which influences the effectiveness of SSRS is the nature

of the processing. The effect of four different fabrication processes on the conductivity of BZY10

was studied by Ricote et al. [220]. The various fabrication processes include (a) SSRS (b)

conventional sintering using powder prepared by solid-state with NiO as the sintering aid (c)

conventional sintering using powder prepared by solid-state reaction and then annealing at a high

temperature of 2200 ℃ (d) spark plasma sintering (SPS). It was discovered that BZY10 prepared

by SSRS as in (a) had the least grain boundary resistance while the resistivity of the other samples

using the other fabrication methods in increasing order are: (c), (d) and (b). This confirms that the

fabrication process does influence the activation energy for proton conduction across the grain

boundaries. This suggests that Ni-decorated grain boundary gotten through SSRS might promote

the conduction of proton across grain boundaries. This phenomenon has been confirmed by Clark

et al. [221] and Costa et al. [222]. However, Han et al. [223] asserted that the addition of NiO on

BZCY based electrolytes affects proton conductivity and dehydration temperature and with time,

ionic conductivity will also be affected. Based on this assertion, they concluded that NiO is

detrimental to the performance of PCFCs.

Even though tremendous success has been recorded in the adoption and application of the SSRS

approach, there are still certain challenges that need to be addressed [224]. One of those challenges

is the crossing over of electrons through the electrolyte or leave residual second phases which

affect the cell performance. The existence of second phases at grain boundaries may negatively

influence the durability of the cell by reducing the mechanical strength of the electrolyte and

exposing it to failure. The highlighted challenges however do not obviate the recommendation and

application of SSRS in the fabrication of P-SOFCs [120,225]. This is because many highly

43
efficient and relatively cheaper PCOM have been developed using the SSRS approach thereby

confirming the efficacy of this approach in PCOM synthesis and fabrication.

Another important area that is vital to the P-SOFC fabrication process is engineering suitable

interfaces between the electrodes and electrolytes. Thermal and chemical incompatibility between

the electrodes and electrolytes can result in gradual delamination of P-SOFC parts which will

consequently depreciate the cell performance or even lead to failure of the cell. To curb this

challenge, some research works have suggested and used interfacial layers to improve the contact

between the electrolyte and electrode layers[95,138,154,226–229].

The predominant technique for fabrication of PCOM based cells is through the traditional pressing

and co-pressing of perovskite oxide powders. In recent years, researchers have investigated and

attempted using tape casting technique for cell fabrication to achieve a larger area, hence higher

performance. In 2017, Jin et al.[223] proposed and successfully fabricated an anode supported

BZCY based cells by tape casting and suspension spraying. This is an upscale in cell fabrication

for PCFCs because it is more established in the traditional O-SOFCs. Hence, more effort is needed

in this capacity to further develop ways to achieve meaningful upscale in the fabrication of PCFCs.

44
5 Prospective for PCFCs

5.1 Identified trends and future guidelines for P-SOFCs

This section presents a summary of recent progress and directions for protonic ceramic fuel cells.

Based on the discussions in the previous sections and recent findings, the progress in the

advancement of protonic ceramic fuel cells can be highlighted as follows:

(a) There has been an increasing propensity and drive towards more compositionally complex

cathode materials which have excellent triple conductivity and are specifically designed

for P-SOFCs. More so, it has been observed that most high-performance cathode materials

always have an element of Co in their composition. Therefore, it will be prudent to assert

that Cobalt containing compounds are promising in achieving a cathode material with an

excellent ORR, especially for low and intermediate temperature P-SOFCs.

(b) There has been a dynamic shift from the use of traditional BCY and BZY electrolyte

materials to electrolytes with more complex compositions such as BCZYYb and BZCY,

with BCZYYb being in the spotlight because of its all-round advantage which involves a

balance in the stability, performance, ease of fabrication and performance.

(c) There has been a remarkable improvement in the performance of P-SOFCs using hydrogen

fuels from about 0.3 W/cm2 to 1.302 W/cm2 at a temperature of 600 ℃ between 2013 and

2019. This represents a hallmark achievement in the advancement of proton-conducting

solid oxide fuel cells.

(d) Attention has been driven towards cathode development for PCFCs through the design of

self-assembled triple-conducting nanocomposite materials.

45
 (e) There has been an increasing interest in the development of high-performance bifunctional

cathode materials which can be used in PCFCs, PCECs, and RePCCs (the RePCC is

addressed in Section 5.1.1).

One of the important future guidelines is the development of PCFCs with high durability under

realistic working conditions. To achieve this, effort need to be intensified to develop P-SOFCs that

can function efficiently at temperatures below 400 ℃. A breakthrough in this regard will facilitate

the commercialization process for PCFCs.

Hydrogen is an ideal fuel for fuel cells, including H-SOFC. However, hydrogen production and

storage efficiently and economically are still challenging. Nevertheless, hydrogen can be generated

in the near future through proton conducting electrolysis cells by using excess energy from

renewable energy sources such as solar and wind energy. However, conventional hydrocarbon

fuels such as natural gas will continue to be a major fuel in the coming decades. Biogas, consisting

of methane, hydrogen, carbon monoxide, etc., will increasingly play more important roles in future

energy supply. Therefore, it is of practical importance to develop H-SOFC running on

conventional hydrocarbon fuels and renewable biogas. Direct hydrocarbon fuel can potentially

help in this capacity and several studies have explored and demonstrated this possibility [82,138].

Stability and durability are also important considerations in P-SOFC development. The important

roles thermal and chemical stability play in the durability of the cell have been addressed in

previous sections. Stability is highly correlated with durability in P-SOFC development.

5.1.1 Reversible protonic ceramic cells

These are energy storage devices that efficiently combine the functionalities of protonic ceramic

fuel cells and protonic ceramic electrolysis cells (RePCC). This innovative idea was borne out of

46
the need to offset the intermittent nature of energy from renewable sources such has wind and solar

which have penetrated the energy market in recent years. The excess/waste energy from renewable

energy sources during their peak periods can be used to convert electrical energy to chemical

energy in the protonic electrolysis cell mode while during periods when the energy demand from

the grid exceeds the supply, the stored chemical energy can be converted directly to electrical

energy in the protonic ceramic fuel cell mode as illustrated in Figure 16. The merits of RePCC are

(a) it is relatively economical than chemical batteries on a larger scale, (b) it has a high round trip

efficiency, (c) it does not require precious metals as catalysts as in the case of reversible polymer

electrolyte membrane electrolysis cells, (d) it directly produces pure and dry hydrogen thereby

saving cost and removing complexities associated with drying and external condensers, among

others.

Figure 16: RePCC operating in (a) protonic ceramic fuel cell mode and (b) protonic ceramic
electrolysis mode. Where HER = hydrogen evolution reaction, ORR = oxygen reduction reaction,
OER = oxygen evolution reaction, HOR = hydrogen oxidation reaction [230]. Copyright 2021,
John Wiley & Sons.

However, despite the numerous advantages of RePCC, one of the major identified challenges to

its commoditization is the paucity in bifunctional electrodes which play a vital role in achieving

47
highly stable and active electrodes with both excellent oxygen evolution reaction (OER) and

oxygen reduction reaction (ORR). High OER in RePCC implies an efficient surface exchange with

proton and electron conduction while a high ORR implies a good adsorptive dissociation and

diffusion of oxygen, coupled with triple conductivity (i.e., involving protons, electrons, and

oxygen ion). All the identified requirements of functional materials cannot be obtained in a single-

phase perovskite oxide material. Although some perovskite materials that possess excellent MIEC

can be used as air electrodes for RePCC, but they lack proton conductivity and are highly unstable

under humid atmospheres [91,231]. Another approach employed for achieving excellent electrode

materials for RePCC is the introduction of electronic conductivity into traditional proton

conductors such as BaCeO3 and BaZrO3 by doping these materials with transition elements and

rare earth metals to achieve materials such as BaCo0.4Fe0.4Zr0.1Y0.1O3-d and Pr0.5Sr0.5Co1.5Fe0.5O5+d.

Although these materials have excellent performances but there is thermal mismatch between these

electrodes and other components of the cell. Hence there need to further consider other material

improvement strategies that can cater for these enumerated challenges. Among those strategies

considered to achieve this feat is the development of nanocomposite electrodes. Recently, Song et

al.[230] presented an interesting and novel perspective based on nanocomposites for advancing

bifunctional reversible protonic ceramic cell electrode materials with relatively outstanding

performances. Cerium and Nickel Oxide nanoparticles were used to embellish the surface of a

nanocomposite electrode comprising Ruddlesden-Popper (RP) and tetragonal perovskite phases.

It was discovered that the RP phases enhanced the proton transfer and hydration while the

nanoparticles expediated the surface oxygen exchange and transfer of oxide ions from the surface

to the major perovskite. This approach promises to create pathway for achieving an optimal

reaction activity in electrolysis and fuel cell electrodes.

48
5.2 PCFC application and scale-up

PCFCs can be employed for stationary applications especially as power supplies for residential

devices such as combined heat and power (CHP) cogeneration systems, and other applications

such as auxiliary power supplies and power sources for vehicles [232,233]. For these applications

to be realized, there is a need for a scale-up. This has been a daunting task particularly due to

various stability issues (such as thermal cycling and chemical incompatibility between the cell

components) and insufficient knowledge about stack design and system integration [234–237].

There have been attempts to increase the active area of P-SOFCs from 0.5 cm2 (often used in the

labs) to over 50 cm2 to explore the feasibility of large-scale production [143]. To achieve a scale-

up, there must be a significant improvement in material advancement, improved fabrication

procedures, and a better understanding of the various key operation mechanisms of the system. In

realizing scale-up in PCFCs, some researchers have reported significant contributions that could

aid in achieving this goal. For instance, Mu et al. [238] presented a unique digital approach which

integrates precise micro extrusion of 3D printing and fast laser processing for achieving several

developmental processes in PCFC fabrication such as sintering, drying, cutting and polishing.

Tarutin et al. [239] also introduced a one-step sintering process for preparing multilayer PCFCs

putting into consideration compatibility of component parts and easier cell preparation methods.

Likewise, the use of dynamic mechanical analysis for the characterization of the thermo-

mechanical behavior of green tapes have been introduced by Mercadelli et al. [240]. This

proposition promises to help achieve optimal lamination viscosity requisite for adhesion between

cell component parts regardless of the adopted tape formulation. Scaling up SOFCs and P-SOFCs

is very challenging because it requires synergy and expertise contributions from disparate

researchers (as observed from some of the scaling up contributing attempts by researchers) from

49
different disciplines such as Material Science, Mechanical Engineering, Electrical Engineering,

Control, and Automation, etc. The aspiration of scale-up in P-SOFC cannot be actualized by a

single research group and this makes it even more complicated coupled with the associated costs.

Hence, government and philanthropic aids might be required to achieve rapid scale-up in P-SOFC

development.

6. Conclusion

The current challenges with the conventional solid oxide fuel cells have driven researchers to

consider investigating proton-conducting solid oxide fuel cells as a viable solution to achieving a

cleaner, more efficient, and cheaper energy alternative. We have presented a thorough review of

the various credible scientific efforts exerted in the development of electrolyte, cathode, and anode

materials for PCFCs. Finally, we have buttressed the prospective for PCFCs by highlighting their

future guidelines and scale-up potentials.

Acknowledgment

M. Ni thanks the funding support (Project Number: PolyU 152064/18E) from Research Grant

Council, University Grants Committee, Hong Kong SAR. B. Chen thanks the National Natural

Science Foundation of China Project (No. 52006150) and Natural Science Foundation of

Guangdong Province (No. 2020A1515010550). Y. Zhang thanks the fellowship of China

postdoctoral science foundation (No. 2021T140471) and the National Natural Science Foundation

of China Project (No. 22109101).

50
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