Bull. Mater. Sci.

(2021)44:287 " Indian Academy of Sciences

https://doi.org/10.1007/s12034-021-02572-6Sadhana(0123456789().,-volV)FT3](012345
6789().,-volV)

Recent advancements on non-platinum based catalyst electrode

material for polymer electrolyte membrane fuel cells: a mini
techno-economic review

DINESH KUMAR MADHESWARAN and ARUNKUMAR JAYAKUMAR*

Department of Automobile Engineering, SRM Institute of Science and Technology,
SRM Nagar, Kattankulathur 603203, India
*Author for correspondence ([email protected])

MS received 2 March 2021; accepted 2 August 2021

Abstract. The crucial component involved in a polymer electrolyte membrane (PEM) fuel cell stack is the catalyst
electrode material which performs a significant role in reaction kinetics and subsequently on the performance. Recent days
have given impetus to the advancements of a relatively cost-effective, yet high-performance electrocatalyst for PEM fuel
cell application. Qualitative studies reveal that significant advancements in the stability and activity of non-platinum
electrocatalysts were achieved that could make a significant contribution on commercializing the PEM fuel cells in a
vast scale. The present paper reviews the non-platinum-based electrode materials used for PEM fuel cell in the past seven
years (2015–2021) and also envisages on the role of novel cost-effective electrode materials. In addition, the paper also
provides a critical snapshot on the advancements of the PEM fuel cell electrode materials in diverse operating
environment.

Keywords. PEM fuel cell; electrodes; non-platinum catalysts; carbon; oxygen reduction reaction (ORR).

1. Introduction 1.1 Components and principle of PEM fuel cell

Energy and environment are mutually interdependent PEM fuel cells comprise multiple layers of composite
constituents that lead to a sustainable development [1]. A materials. Following are the key components of a PEM fuel
relatively highly efficient and sustainable energy system must cell illustrated in figure 1 [20].
be both cost-effective and must also produce minimal 1.1a Membrane The membrane (proton conducting) is a
harmful emissions. The limitation with the most credentialed uniquely engineered material that appears to be modified
renewable platforms, such as solar and wind energy power Teflon used in home kitchen. The membrane conducts only
systems, is because of the discrepancy between energy sup- the positive ions and blocks the electrons [21,22]. Being the
plies and demands [2–6] due to their intermittent operation integral PEM fuel cell component, the membrane allows only
nature. Fuel cells are sustainable and reliable energy systems appropriate ions (positive ions) to flow from anode to cathode
which operate on hydrogen (cleanest fuel) and are potential [23].
alternatives to the noxious fossil fuel-based [7,8] generators.
Due to lack of combustion or emission, there is tremendous 1.1b Catalyst layer: Catalyst layer (CL) is the core constituent
electrical efficiency than conventional generators of parallel in PEM fuel cell that drives the electrochemical kinetics and
size and rating [9–14]. Various types of fuel cell technologies activity [24]. Hydrogen fed at anode catalyst-side is oxidized
are polymer electrolyte membrane fuel cell (PEMFC), solid and generates electrons and protons (hydrogen ions). On the
oxide fuel cell (SOFC), alkaline fuel cell (AFC), phosphoric contrary, the oxidant is fed to cathode catalyst-side on another
acid fuel cell (PAFC) and molten carbonate fuel cell (MCFC) side where the reduction takes place. A PEM fuel cell’s anode
[15–17]. Among these fuel cell technologies, PEM fuel cells and cathode reactions are as follows:
are widely used owing to their distinct features, such as quick
startup, low-operating temperatures (60 to 80!C), dynamic Anode : H2ðgasÞ ! 2Hþ $
ðaqÞ þ 2e ; Eao ¼ 0 V;
response and high power density [18]. In addition, PEM fuel 1
cell has significant implications on a nation’s economy by Cathode : O2ðgasÞ þ 2Hþ $
ðaqÞ þ 2e ! H2 OðliqÞ ;
2
reducing their rely on imported crude oils and thereby
strengthening the energy security [19]. Eco ¼ 1:23 V:
287 Page 2 of 12 Bull. Mater. Sci. (2021)44:287

For instance, Ehelebe et al [34] reported that the effect of

The optimal standardized potential (Eo ) for a PEM fuel
electrode parameters influences the stack performance. An
cell at 298 K reaction kinetics is 1.23 V for liquid water as
electrode system should always be in contrast with the
by-product and 1.18 V for gaseous water as by-product.
recent state-of-art developments to provide holistic insights
1.1c GDL: The gas diffusion layer (GDL) electrically [35].
interconnects with the current collector and the catalyst Figure 2 represents the electrochemical reaction of
layer to facilitate the reactant transport to the electrocatalyst PEM fuel cell electrode (cathode side) to produce water
site. In addition, the GDL also aids in the removal of pro- along with the proton and electron transport. It is still
duct water [25]. It usually comprises of two layers, namely essential for the investigation of electrode materials for
hydrophobic layer made up of polytetrafluoroethylene the PEM fuel cell applications, as the research on other
(PTFE) and macroporous layer which is made up of carbon components have already progressed much [36]. It is
paper/carbon cloth concealed with the microporous layer. evident from figure 3 that the conventional electrodes
Reactant gases diffuse through the GDL pores. The (platinum group of metals) account to 43% of overall
hydrophobic PTFE held pores open, inhibiting the excess PEM fuel cell costs [37].
water accumulation [26,27]. The integration of GDL and Although platinum is found to be a broadly employed
catalyst layer is termed as electrode layer. Ironically, in case electrode, it is attributed to its characteristics, such as
of the catalyst-coated membrane (CCM), the catalyst is reactant activity, chemical stability and high current den-
coated directly onto the membrane. sity. Ironically, the limitation with Pt-based electrodes is its
high cost and CO poisoning [38] which limit its commer-
1.1d Bipolar plates: Each cell within the stack is sand-
cialization. In recent days, numerous researches signifi-
wiched across two bipolar plates, which separates it from
cantly contributed towards seeking optimal alternative
nearest cells and provides the stack with electrical con-
electrode materials for PEM fuel cell application. A con-
duction and also provides robustness to the stack. The plates
siderable number of literatures have already contributed to
normally have a ‘flow field’ within them, that are machined/
the optimized performance and durability of other key
stamped with a set of channels which facilitates the gas flow
components of PEM fuel cell, such as GDL, membrane and
evenly through membranes [28,29].
bipolar plates [39–41]. In the present work, the review is
1.1e Gaskets: Membranes in each stack are sandwiched limited to assessment on innovations in cost-effective non-
between couple of bipolar plates along with gaskets that are platinum group of metal (PGM) electrodes for PEM fuel
usually made of rubber polymers, around this membrane cell applications in the last seven years. Section 2 describes
assembly that makes a gas tight seal [30]. the required attributes for an electrode to be functionally
Electrode is by far the most critical and expensive effective and it also illustrates about the major challenges
material among the various PEM fuel cell components encountered for a PEM fuel cell electrode during operation
discussed and its properties always said to have critical i.e., critical losses. Section 3 provides short description on
impacts on efficiency and durability of the stack [31–33]. the conventionally used Pt and Pt-alloy electrode materials

Figure 1. Basic components and working principle of a PEM

fuel cell. Reprinted from reference [20]. Copyright 2019 with Figure 2. Electrochemical reaction of PEM fuel cell electrode
permission from Springer. (cathode side) to produce water.
Bull. Mater. Sci. (2021)44:287 Page 3 of 12 287

In PEM fuel cell reaction kinetics, the oxygen reduction

reaction (ORR) is sluggish compared to the hydrogen
oxygen reaction (HOR) by a factor of 6–7 [52] and subse-
quently, the challenge is to develop a potential electrode for
ORR [53]. In contrast with other electrode materials, Pt has
the highest degree of activity for ORR and thus, often
positioned at the top (peak) of the ‘volcano’ plot given in
figure 4, which is described by the Sabatier theory [54].
The electrode performance is determined by the current
at an obtained voltage (Vfc). i.e., normalized current density
measured, also known as mass activity, which is most
widely used figure to compare various electrodes [55]. The
role of electrode is incredibly significant in minimizing the
activation losses and subsequently, contributing towards a
Figure 3. Cost contribution of PEM fuel cell stack components
better performance [56].
[37].
The actual cell potential is computed from its ideal
potential and is due to the various irreversible losses which
and their hurdles for not being much successful in are termed as polarization. Polarization curve given in
commercial market. Followed by section 3, section 4 figure 5 [57] is the fundamental kinetic law for fuel cells,
assesses researches attempted to develop inexpensive non- which is a plot of current density and cell potential. With
PGM electrode materials for PEM fuel cell. We describe the the help of polarization curve, the influence of three cate-
technology to adapt PEM fuel cell with electrode materials gories of loss is always easy to discern [58]. Multiple
rather than PGM metals and their significance. Section 5 phenomena leading to irreversible losses in a PEM fuel cell
summarizes the overall review and the snapshot on the are the activation polarization (Vact), the ohmic polarization
recent advancements in PEM fuel cell electrodes. (Vohmic) and the mass transportation polarization (Vcon) [59].
At the activation polarization region, the reaction kinetics
are said to be sluggish. Ohmic polarization region is the
2. Functional attributes of a PEM fuel cell electrode liner region where the fuel cells predominantly operate, and
at mass transportation region due to the inability of the fuel
PEM fuel cell electrode is considered as the heart of the fuel cell to match the reactant supply and demand. Activation
cell stack and it indeed enables electrons to carry continu- losses (Vact) eventually lead from activation potential of the
ally from the anode to cathode [42,43]. In compliance with electrochemical processes that normally occurs at the
this function, electrodes for PEM fuel cell are ought to have electrodes i.e., sluggish electrode kinetics. The activation
certain properties (table 1) to achieve overall better per- losses predominantly depend on catalyst material,
formance of the fuel cell stack. Researchers seek to develop microstructure, reactant activity and utilization, and current
a PGM-free catalyst and firmly focussed on meeting the density [60]. The ohmic losses (Vohmic) result from the ionic
crucial functional attributes at better performance and cost- and electrical resistances of electrodes and also the contact
effective [43]. resistances. These losses are directly proportional to the

Table 1. Functional attributes of a PEM fuel cell electrode.

Attributes Functions References

Activity The reactant must facilitate the reaction kinetics of electrodes. [44]
Selectivity To develop intended product and minimize parasitic products at the output. [45]
Stability, mechanical and To be robust and withstand the PEM fuel cell operational environment, such as [46]
chemical durabilities strong oxidizing agents, reacting radicals, an acidified atmosphere and
temperature rates which fluctuate faster at higher voltage.
For reliable performance and durable life under oxidation.
Resistance to poisoning Immune against impurities present in the fuel cell and in the feed gases. [47]
Ionic and electronic To carry charged ions and better electrical output. [48]
conductivities
High degree of porosity For effective transportation of gases. [49]
Design attributes Low internal electric losses, low cost of electrode, constant composition [50,51]
electrolyte and ecologically acceptable fuels.
287 Page 4 of 12 Bull. Mater. Sci. (2021)44:287

towards economical material, but also towards an effective

performance along with substantial robustness [65].

3. Platinum-based electrodes

Platinum (Pt) is the most effective electrode material for

both HOR and ORR, where Pt nanoparticles are assisted by
carbon nanosphere [66]. Since reactions of the PEM fuel
cell are structural-sensitive reactions that are more con-
centrated on crystal facets, highly regulated morphological
nanoparticles with highly active crystal facets are efficient
in application of PEM fuel cell electrode [67,68]. Stability
should also be considered in the electrode development, in
addition to performance. The key cause of loss in electrode
performance of PEM fuel cell is the Ostwald ripening
Figure 4. Volcano plot of key electrode materials for PEM fuel [69–71] process which is accelerated by electrochemical
cell. Reprinted from reference [54]. Copyright 2014 with permis- dissolution and redeposition of dissolved Pt on the surface
sion from licensee Beilstein-Institut. of electrode. Due to the disparity in the surface free energy,
thermodynamic chances of agglomeration of smaller parti-
cles to larger particles being high; the larger particle sizes
contribute to less efficient electrochemical surface area,
thus, minimizes mass activity and catalytic efficiency
[70,71]. The chemical synthesis of deposition of Pt
nanoparticles into carbon, supports and ensures to obtain
relatively small particles, thus, effectively eliminating
Ostwald ripening of Pt nanoparticles [72–76].
Transitional metal alloy Pt has been found to greatly
boost the slow ORR kinetics for the cathode due to geo-
metrical and electronic attributes [77]. Pt–Co/C, Pt–Ni/C,
Pt–Cr/C and Pt–Cu/C alloyed nanoparticles are few exam-
ples that are successfully prepared for fuel cell electrode
application [78–81]. A comparative study demonstrated that
although this form of alloying considerably enhances ORR
Figure 5. Polarization characteristics of a typical PEM fuel cell operations, common alloy materials, such as Co, Ni and Fe
[57]. are appeared to be leached from the electrode nanoparticles
in a highly acidic PEM fuel cell environment [82,83]. ORR
occurring at the PEM fuel cell cathode is catalysed by the Pt
current density [61]. Mass transportation losses (Vcon) are loadings to greatly minimize the over potential loss [84].
result of reactant rate limitations of finite masses occurred The standard loss is the activation of over-potential, on
due to the reduction in concentration of the gas at the which their magnitude highly relies on the reaction kinetics,
interface surface of electrode–electrolyte [62]. In addition more precisely on the size of exchange current density [85].
to the activity of catalyst measurement cost and durability; Thus, the enhancement of kinetic reaction efficiency is
overall efficiency must also be calculated to assess the accomplished by raising the current density that relies on
commercial value, strength and stability of the electrode the activation, reaction concentration and reaction sites,
[63]. barriers and temperature. These variables inhibit large-scale
Following equation defines the fuel cell output voltage marketing and have led to intensive research towards
(Vfc) of single PEM fuel cell. inexpensive, highly active and stable non-PGM electrodes
[86].
Vfc ¼ Eo $Vact $Vohmic $Vcon :
where Eo is the standard potential of fuel cell.
Numerous researchers have studied how expensive 4. Non-pt electrodes
electrode materials can be substituted, while guaranteeing
that the cells persist to augment primary efficiency metrics PGMs are quite expensive, their cost is subjected to
(durability and power density) [64]. Researchers eye to volatility, they are available from only very few sources and
develop PGM free electrodes which not only contributed their cost does not scale with larger production volume.
Bull. Mater. Sci. (2021)44:287 Page 5 of 12 287

Hence, for long-term accomplishment of fuel cells, PGM- 4.1 Fe-based electrodes
free catalysts need to be developed. It is for this reason,
researchers have strategically targeted their focus on their Vinayan et al [95] developed an active, robust, non-
work on the eradication of PGM from the fuel cell system, platinum metal electrocatalyst that has been synthesized
and its replacement with a high-performance, durable PGM- from a precursor of the electrode at high temperatures,
free electrocatalyst for PEM fuel cells. Although substantial which include Fe–, N– and S-charged salt co-doped with
technological advancements have been made in various graphene that forms structured electrode made ideal for
respects in developing Pt electrodes, there remain obstacles PEM fuel cell application. The material synthesized is an
to commercialize fuel cells to compete with conventional electrode of metal–nitrogen–sulphur group and has an open
sources, where the cost, efficiency and durability of fuel matrix structure (4 mg cm-2) with Nafion 212 as elec-
cells are yet to be enhanced [87]. This drives researchers to trolyte, regulated by the silica-templating process. The
work on developing a substitute to address the criterion that Fe–NSG electrode was shown to be sustainable, which at
PEM fuel cell electrode material demands [88]. Table 2 [32] 0.5 V provides a peak power density of 225 mW cm-2
provides the classification of various platinum and non- (80!C) with promising stability and high current density.
platinum electrode materials for PEM fuel cell. A hybrid Fe–N–C electrode from a bi-metal-organic
The quest for developing low-cost, high-performance frame (Zn/Fe-ZIFs) developed by Liu et al [96] was one of
PEM-fuel cell electro-catalysts began approaching with two the best non-noble metal electrodes ever reported on ORR
different strategies. The first way is to lessen the use of in acidic and alkaline environments. Fe–NC-20-1000 loa-
catalysts by enhancing Pt usage of the catalyst layers [89]. ded with catalyst loading of 0.75 mg cm-2 and ZIF-7 pre-
This could be executed by employing relatively cost-ef- cursor exhibited a half-wave potential ORR activity of
fective Pt alloys (such as Co, Fe, Mn, etc.) and/or through 0.770 V which is close to that of the 0.827 V for Pt/C
using unique supportive materials to enable deposition of Pt in acidic medium. The power density exhibited is 870 mW
nanoparticles [90]. cm-2 at 130!C which is 10% positively higher than Pt/C’s
Over the past decades, although the Pt loading was ORR.
reduced considerably to about 0.4 mg cm-2 [91], ironically, Bhange et al [97] reported a Pt-free iron-based electrode
the overall cost of the electrode has not been reduced sig- doped with sulphur and scrolled graphene (P12-900) as a
nificantly, especially for the long-term way [92]. There is potential ORR electro catalyst. The single PEM fuel cell
also an approach attempted to recycle the Pt electrodes to using Nafion with isopropyl alcohol (IPA) as electrolyte
limit the large-scale production expenses. The attempt was under catalyst ratio of 0.5 demonstration employed with
made by Balva et al [93] to recycle platinum by leaching it P12-900 electrode (loading of 2 mg cm-2) produced peak
via coupling with chlorine/ionic liquids. Though the recy- power density of 345 mW cm-2 and is equivalent to the
cled Pt electrode helps reducing large scale production cost, state-of-the-art Pt/C cathode which is 322 mW cm-2.
the sluggishness persist as a barrier on performance Through its unrivalled propensity to accelerate electrode
improvement. Those approaches were not found to be sig- reaction, the prepared PGM free electrode can therefore,
nificantly contributed towards reducing the overall cost of serve as a viable alternative to substitute expensive metal
PEM fuel cell. As a consequence, there has been an incli- electrode for PEM fuel cell.
nation towards research as a third approach on producing From last few decades, iron-based electrodes were found
non-PGM electrodes. Developing high-performance, non- to be potential alternative for PGM-free electrode, in a
PGM-based electrodes thus, appear to be the key path to the research by Khan et al [98], Fe-doped C12A7 (a maynite
sustainable manufacturing of PEM fuel cell applications. electrode synthesized of nanoparticles) was developed with
However, till date, activity and stability of non-PGM elec- A201 Tokuyama as electrolyte membrane. The developed
trodes are inferior to Pt electrodes [94]. electrode was a composite, cost-effective, exceptionally
durable, active and precious metal-free with catalyst load-
ing of 0.1 mg cm-2. The maximum power density reached
up to 275 mW cm-2 at a potential of 1.03 V operated at
Table 2. Various PEM fuel cell electrode materials [32]. 80!C, where for the conventional Pt/C electrode, the power
density was 245 mW cm-2 at the same operating condi-
PGM-based Platinum alloy-based Non-PGM tions. The results are evident that Fe-doped C12A7 would
be an incredibly alluring precious metal-free electro
Electrode material catalyst.
Pt Pt–Cr/C Fe–N–C
In high-temperature polymer electrolyte membrane fuel
Pd Pt–Ni/C C
Rh Pt–Co/C Ionic liquids
cells (HT-PEMFC), the ORR activity of Pt-based electrodes
Ru Pt–Cu/C Graphene is weak because of the poor resistance of Pt-based elec-
Ir trodes towards phosphate ions. Fe and N co-functionalized
Os with carbon (Fe–N–C) exhibits resistance to phosphate ions
and act as a potential option for PEM fuel cell [99–101].