international journal of hydrogen energy xxx (xxxx) xxx

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Coated stainless steel as bipolar plate material for

anion exchange membrane fuel cells (AEMFCs)

Sebastian Proch*, Mikael Stenstro

€m, Lennart Eriksson, Jan Andersson,
€blom, Anna Jansson, Jo
Gustaf Sjo €rgen Westlinder
Sandvik Materials Technology, Sandviken, Sweden

article info abstract

Article history: Low-temperature anion-exchange membrane fuel cells (AEMFCs) are gathering increased
Received 18 June 2018 attention because they facilitate the use of non-precious metal catalysts, which might
Received in revised form drastically reduce costs compared to low-temperature proton exchange membrane fuel
11 April 2019 cells (PEMFCs). Metallic, e.g., stainless steel, bipolar plates (BPPs) present a cost-efficient
Accepted 12 April 2019 solution for this type of cell. However, anodic film formation at high positive potentials
Available online xxx (approx. þ1.5 V vs. RHE) on uncoated metals/stainless steels leads to high interfacial
contact resistance (ICR) of the BPP once exposed to such a potential. A potential of þ1.5 V
Keywords: vs. RHE is commonly reached under local and global hydrogen starvation, which rules out
Carbon coating the use of uncoated metals in AEMFCs. We have investigated the ICR change and oxide film
Bipolar plates (BPPs) formation of several materials under simulated fuel cell operating conditions and found
Anodic films that suppression of anodic film formation and, in turn, low ICRs can be achieved by carbon
Anion-exchange membrane fuel coating of stainless steels.
cells (AEMFCs) © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Interfacial contact resistance (ICR)
Glow-discharge optical emission
spectroscopy (GD-OES)

Introduction hydrogen (anode) side: 2H2 þ 4 OH / 4H2O þ 4 e (HOR)

Platinum group metals (PGMs), e.g., Pt, Ir, etc., are among the
oxygen (cathode) side: O2 þ 2H2O þ 4 e / 4 OH (ORR),
rarest elements in Earth's crust [1], however, they are indis-
pensable electrocatalysts in proton-exchange membrane which leads to a total of 2H2 þ O2 / H2O. The anion-
(PEM) technology, i.e., fuel cells [2] and electrolyzers [3,4]. The exchange membrane (AEM) is not electrically conductive,
dependence on scarce and, therefore, expensive PGMs can be and electrons, obtained from the hydrogen oxidation reaction
alleviated by the introduction of anion-exchange membranes (HOR) are transferred from the anode to the cathode through
which facilitate alkaline fuel cells and, in turn, the use of an external circuit, where electrical work can be extracted.
inexpensive base metals [5e9]. A schematic overview of an Poor electrical contact between the layers in Scheme 1 leads to
AEMFC is presented in Scheme 1 and its electrode reactions increased resistances in the system and, thus, lower voltages,
are and, in turn, lower efficiency.

* Corresponding author.
E-mail address: [email protected] (S. Proch).
https://doi.org/10.1016/j.ijhydene.2019.04.122
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
2 international journal of hydrogen energy xxx (xxxx) xxx

Scheme 1 e Overview of the main constituents and charge carrier flows in an anion-exchange membrane fuel cell (see text).
The “question marks” at the GDL/BPP interface present its variability upon potential changes (carbon corrosion/oxidation,
anodic film formation).

Many metals, and, hence, metallic bipolar plates (BPPs) Fig. 1 left shows the electrochemical situation for local
show a potential dependent surface structure in aqueous hydrogen starvation in an AEMFC, which is in analogy to the
environments, symbolized by the purple question marks in same situation in PEMFCs. Water condensation in the anode GDL
Scheme 1. This is, because, they are oxidized at positive (gas diffusion layer) can lead to hydrogen starvation of a part of
potentials leading, oftentimes, to anodic (oxide) film growth. the anode CL (red part on the anode side in Fig. 1 left). In this
Film growth gives rise to high interfacial contact resistance region, the absence of hydrogen leads to reductive conditions
(ICR) since metal oxides frequently are semiconductors or since surrounding parts supply the hydrogen starved region with
insulators [10e13]. The situation is more severe in alkaline electrons due to the high in-plane conductivity of the bipolar
environments because metal oxides tend to be more stable plate. Usually, ORR takes place in this region, which delivers
under those conditions [14]. High positive (anodic) potentials hydroxide ions for carbon corrosion in the adjacent cathode re-
can occur transiently during fuel cell operation at the cathode gion. There, the cathode potential can go up to between þ1.5 and
and anode side, which is explained in detail in the following. þ2 V vs. RHE and the cathode is degraded locally. The hydroxide
The HOR in the AEMFC generates water in stoichiometric and electron flow in the opposite direction from normal opera-
amounts at the anode (see above), thus, making water man- tion is known as “reverse” current and the degradation mode
agement more challenging than in proton-exchange mem- accordingly as “reverse” current degradation. This mode was
brane fuel cells (PEMFCs) since anode flooding can frequently discovered by Reiser et al. and is also very prominent during
occur [15,16]. The risk for anode flooding is further increased startup and shutdown (SUSD) cycles when an air front, from
when one considers that most polymers used in AEMFCs ingress during downtime, moves through the anode CL [22].
require high relative humidity to achieve their high ionic The electrochemical situation known as global hydrogen
conductivity [17,18]. The condensation of liquid water drop- starvation is presented in Fig. 1 right. Blockage of hydrogen at
lets in the anode compartment might lead to blockage of the inlet leads to an anode CL which is completely devoid of
hydrogen pathways in certain areas of the anode. Such con- hydrogen and, in this case, electrons for oxygen reduction at
ditions are referred to as hydrogen or fuel starvation and are the cathode are supplied by carbon oxidation. The potential
known to have drastic consequences on carbon stability in goes up to between þ1.5 and þ2 V vs. RHE and carbon struc-
PEMFCs [19,20]. Carbon corrosion (oxidation) can be described tures are degraded globally, i.e., in the whole anode
by the following equations with a reversible potential of compartment of the fuel cell [19,20].
þ0.2 V vs. RHE (reversible hydrogen electrode) [21]: In summary, transient fuel cell operation (hydrogen star-
vation) creates conditions relevant for anodic film growth and,
carbon oxidation reaction (acidic): C þ 2H2O / CO2 þ 4 Hþ þ 4 e concurrently, high ICR might be observed at both BPP/GDL
(COR) interfaces (see Scheme 1). A common architecture of metallic
BBPs, in which two BPPs are joined together with the coolant
carbon oxidation reaction (alkaline): C þ 4 OH / CO2 þ passed between them [23], might even lead to the formation of
2H2O þ 4 e (COR) four anodic (oxide) films (see Fig. 2).
In this context, it is instructive to briefly review oxide film
There are two main types of starvation, i.e., local and growth on single metals and passivating alloys. Conway [24]
global, where the former affects the cathode [22] and the latter describes the following mechanisms in the early stages of
the anode side [19,20], as follows. film formation,

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
 international journal of hydrogen energy xxx (xxxx) xxx 3

Fig. 1 e Left. Local hydrogen starvation. Part of the anode CL is deprived of hydrogen (red region on the anode side) and HOR
cannot take place. The high in-plane conductivity of the BPP, however, supplies electrons to this region and creates a
“reductive” atmosphere. In this region, ORR can take place which supplies hydroxide ions for carbon corrosion at the
adjacent cathode region, where the potential can reach þ1.5 to þ2 V vs. RHE. Right. Global hydrogen starvation. The
complete anode CL is deprived of hydrogen (red region) and supplies electrons for ORR at the cathode by carbon oxidation.
The potential at the anode side can reach between þ1.5 and þ 2 V vs. RHE under such conditions. (For interpretation of the
references to colour in this figure legend, the reader is referred to the Web version of this article).

(a) “Dissolution and Precipitation”, i.e., the metal is dissolved, After sufficient growth of an oxide film the so-called “high-
undergoes hydrolysis, and the hydrolyzed species pre- field” or “Mott-Cabrera” mechanism (field-assisted ion sepa-
cipitates on the metal surface (e.g., Zn); ration) can lead to thick film growth, often potential-
(b) “Nucleation and Growth”, i.e., oxide film growth in the dependent, by metal cation migration towards the metal
absence of metal dissolution (e.g., Ni, valve metals like oxide/electrolyte interface and OH/O2 migration towards
Ti, Ta, Zr); and the metal oxide/metal interface. This is especially common
(c) “Place-Exchange”, i.e., initial adsorption of O/OH in a 2D for very stable oxide films with low conductivity, e.g., valve
fashion and subsequent interchange between metal metal oxides [25,26].
atoms and O-species in the adlayer (e.g., noble metals Anodic film formation on passive alloys containing Cr has
like Pt, Au). been reviewed by Olsson [14]. The main point is that those
alloys (e.g., Fe, Ni) owe their corrosion resistance to the for-
mation of a thin chromium oxide film. The thickness of which
is linearly dependent on applied potential. Significantly
thicker films are formed in alkaline environments due to
higher oxide stability. Moreover, iron oxides are more stable at
high pH, while Cr becomes more soluble, giving rise to
Fe-enriched oxide films on stainless steels.
It is clear from the discussion that alkaline solutions at
high positive (anodic) potentials are very challenging envi-
ronments to maintain low ICR values on uncoated metallic
BPP. Anodic film growth has been studied on 304L, a typical
stainless-steel grade, and was found to be rapid with 90% of
total film growth taking place within the first minute [27].
Therefore, we elucidate the question marks in Scheme 1 by
investigating film formation and ICR evolution of uncoated
metals at up to þ1.5 V vs. RHE in a simulated AEMFC envi-
ronment (aqueous sodium hydroxide solution) and compare
Fig. 2 e Common metallic bipolar plate architecture which their behavior to a carbon-coated stainless steel BPP.
joins two plates for the anode and the cathode side. This
facilitates the use of different flow fields at the anode and
the cathode [23]. Water is passed as a coolant between the Experimental
plates and, therefore, the “active” and the coolant side of
the plate is exposed to aqueous media. Under hydrogen Materials
starvation conditions there are four interfaces which might
exhibit anodic film growth, (1) anode GDL/anode BPP; (2) Overview
anode BPP/coolant interface; (3) coolant/cathode BPP All materials investigated in the present study are presented in
interface; and (4) cathode BPP/cathode GDL interface. Table 1. Nanoflex is a stainless-steel grade that has been

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
4 international journal of hydrogen energy xxx (xxxx) xxx

Table 1 e Overview of the materials investigated in this contribution. 304L, 316L, and “Nanoflex” are typical stainless-steel
alloys while San75 is a typical stainless Ni alloy. 316L Coat is a carbon-coated stainless steel which is imagined to be used
as BPP material in AEMFCs (see above).
Ti Grade 2 304L 316L Nanoflex San75 316L Coat
B (wt%) e e e 0.0012 0.003 Carbon-Coated 316 L
C (wt%) e 0.08 0.035 0.008 0.02
N (wt%) e 0.1 e 0.004 0.03
Al (wt%) e e e 0.39 0.94
Si (wt%) e 0.75 1 0.17 0.48
P (wt%) e 0.045 0.045 0.017 0.015
S (wt%) e 0.03 0.03 e 0.01
Ti (wt%) 100 e e 1 2.7
V (wt%) e e e 0.027 e
Cr (wt%) e 20 18 11.7 16.9
Mn (wt%) e 2 2 0.41 0.74
Fe (wt%) e 65 60.89 71.4678 8.8
Co (wt%) e e e 0.041 e
Ni (wt%) e 12 15 8.9 68.132
Cu (wt%) e e e 1.99 e
As (wt%) e e e 0.004 e
Nb (wt%) e e e 0.01 1
Mo (wt%) e e 3 3.85 0.2
Ta (wt%) e e e e 0.03
W (wt%) e e e 0.01 e

developed by Sandvik Materials Technology and it replaces Ni reversible hydrogen (RH) reference electrode (Hydroflex, Gas-
and Cr, in parts, by Cu, Mo, and Ti. Production of the carbon- katel) and a Pt counter electrode. The electrolyte was not gas-
coated 316L steel is presented briefly below. The materials purged during the measurements. A PGSTAT204 potentiostat/
were cut into 3 cm  9 cm strips and sonicated in acetone, galvanostat (Metrohm-Autolab) was used for the following
ethanol, and distilled water (4.4 MUcm, referred to as water in measurement protocol:
the following) for 10 min each at room temperature immediately
before use. (i) open circuit potential (OCP) determination for 600 s
(ii) cyclic voltammogram (CV) between ±0 and þ 1.5 V vs.
Carbon-coated 316L RHE starting from OCP in a positive direction at a scan
The carbon-coating process of stainless steel and the detailed rate of 0.05 V-1 (6 cycles)
characteristics of the coating used in this contribution are (iii) OCP determination for 120 s
proprietary and, therefore, cannot be discussed in detail. (iv) CV between ±0 and þ 1.5 V vs. RHE starting from OCP in
Briefly, a 316L stainless-steel strip is subject to various a positive direction at a scan rate of 0.02 V-1 (6 cycles)
cleaning procedures, including plasma-etching, to remove the (v) OCP determination for 120 s
passive/oxide layer and ensure high contact resistance and (vi) CV between ±0 and þ 1.5 V vs. RHE starting from OCP in
good adhesion properties of the coating. The steel is then a positive direction at a scan rate of 0.01 V-1 (6 cycles)
coated with a metallic adhesion layer and, subsequently, the (vii) OCP determination for 120 s
carbon coating is applied. The process is carried out in a high-
throughput physical vapor deposition (PVD) coating line. After steps (i)-(vii) the sample was rinsed with water, dried
in a nitrogen stream and investigated for its interfacial contact
Electrochemical experiments resistance (ICR) and its surface film composition by glow
discharge optical emission spectroscopy (GD-OES), see below.
Electrolyte preparation
The anodic film growth of the materials from Table 1 was Characterization techniques
tested in two different electrolytes, namely aqueous sodium
hydroxide (NaOH) at a pH of 11 and of 14.5. An NaOH solution Interfacial contact resistance (ICR) determination
of pH 14.5 (3.16 M) was prepared by weighing 63 g of NaOH into Fig. 3 shows the ICR measurement setup used in this inves-
a 700-ml polypropylene beaker and filling up to 500 ml with tigation. The sample strip was exposed to the electrolyte so-
water. 158 ml of this solution were pipetted into another lution in a circular spot with an area of 3 cm2. The rest of the
polypropylene beaker and filled up to 500 ml with distilled sample was covered by an insulating paper mask, in the size
water to yield an NaOH solution of pH 11. of the GDL, in the front and in the back so it was possible to
obtain the ICR of the corroded and the pristine side in a single
Electrochemical setup/measurement protocol measurement. All tests were carried out at a clamping pres-
3 cm2 of the cleaned sample strips were exposed to the elec- sure of 1.40 MPa. The applied method is similar to the one
trolyte at 353.15 K (80 C) in a commercial polytetrafluoro- described by Papadias et al. [28], however, with slight modi-
ethylene (PTFE) cell (FlexCell, Gaskatel) equipped with a fications as described below.

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 3 e Left. Schematic of the interfacial contact resistance (ICR) measurement setup used in this contribution. The metallic
BPP is sandwiched between two GDLs (MGL370, AvCarb Material Solutions) and held between two gold-coated copper
contacts at a clamping pressure of 140 Ncm¡2. The ICR of both GDL/metallic BPP interfaces can be measured using spring-
loaded contacts. Right. Image of the ICR measurement setup used in this contribution.

Au-coated copper contacts are pressed together by a power In the present investigations, GD-OES profiles were recor-
frame since contact resistance is dependent on the applied ded on a GDA750 HR from Spectruma Instruments GmbH
force. A current density of 1 Acm2 is applied to the setup. The (Germany). The instrument was set up to run at 700 V/20 mA/
voltage drop between the copper contacts is measured for (a) 3.5 hPa. The surface of the sample was sputtered using Argon
the carbon GDLs (top and bottom) and (b) the metallic BPP ions and the purity of the gas was higher than 99.9999%. The
sandwiched between the two GDLs (see Fig. 3 left). The analyzed area was 4 mm in diameter and the depth profiles
contribution of the GDLs, measured in (a), is used to evaluate were recorded to a depth far below the zone affected by the
RGDLtop =BPPtop and RBPPbottom =GDLbottom from (b), as follows. electrochemical treatments. Per ISO 16962 [29] and 25138 [30]
The total resistance in (a) is given by the thickness of the oxide layer is defined as the depth at
which the oxygen content drops to 50 mass% of the initial
Rtot ðaÞ¼ RCu=GDLtop or bottom þ RGDLtop or bottom; bulk þ RCu=GDLtop or bottom oxygen concentration. The metal concentration can be used
¼ 2RCu=GDLtop or bottom for the determination of the film thickness in the same way,
i.e., using the thickness at 50 mass% of the final metal
assuming the bulk resistance of the GDL, RGDLtop or bottom; bulk is concentration.
negligible, i.e., (a) provides values for RCu=GDLtop and RCu=GDLbottom , GD-OES measurements were performed within 24 h after
respectively. In (b) the total resistance is given by the electrochemical experiments.

Rtot ðbÞ ¼ RCu=GDLtop þ RGDLtop =BPPtop þ RBPPbulk þ RBPPbottom =GDLbottom

þ RGDLbottom =Cu Results and discussion
¼ RCu=GDLtop þ RGDLtop =BPPtop þ RBPPbottom =GDLbottom þ RGDLbottom =Cu
In-situ (electrochemical) characterization
assuming, again, the bulk resistance to be negligible. Since
the area is well-defined in the measurement and a current Titanium grade 2
density is applied the resistances can be evaluated as area Steps (i) to (vii), see “Experimental”, have been carried out for
dependent quantities, known as interfacial contact re- each sample presented in Table 1. Fig. 4 depicts cyclic vol-
sistances (ICR). tammograms of titanium grade 2 recorded at a scan rate of
0.01 V-1. The current densities detected at pH 11 are much
Glow-discharge optical emission spectroscopy (GD-OES) smaller than at pH 14.5. The rising oxidation current density
towards higher potentials is unlikely to be due to oxide film
GD-OES is a method for the determination of the chemical formation since Ti oxidation in the thickness observed by GD-
composition of surface layers as a function of depth but it is OES (see Fig. 5 and Table 2) requires considerably larger cur-
also frequently used for bulk analysis. The method is very rent densities. The film is rather formed in the first sweep (not
sensitive for low concentrations and depth resolution at the shown) and not removed after that. The currents observed in
nanometer level. In principle, all elements can be analyzed Fig. 4 may be caused by the oxidation/reduction of defects in
quantitatively, including all light elements such as O, N, Cl, C, the formed TiOx film [31].
and even H. Oxygen evolution via [32]

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
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6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e Cyclic voltammograms (CVs) of titanium grade 2, 304L, 316L, Nanoflex, San75, and 316L Coat (Table 1) in aqueous
NaOH (pH 11 and 14.5) recorded at 353.15 K (80 C) at a scan rate of 0.01 Vs-1 ([vi] see “Experimental”).

Stainless-steel grade 304L

4 OH / O2 þ 2H2O þ 4 e (1)
Fig. 4 shows cyclic voltammograms of 304L (Table 1) recorded
has a reversible potential of þ1.23 V vs. RHE [33,34] and at a scan rate of 0.01 V-1. The sharp onset of current density at
might, thus, be observed above this potential, however, a clear þ1.46 V vs. RHE in the pH 14.5 case (blue trace) is attributed to
onset is not exhibited and the current densities of Ti are much oxygen evolution per eq. (1) [32]. Massive oxygen evolution is
lower than observed on other samples (Fig. 4). The Pourbaix not observed at pH 11.
diagram of Ti predicts that there is no electrochemistry, i.e., Although, this steel grade is an alloy containing nine
constituents it can be approximated to be a ternary alloy
change of oxidation state, metal ion leaching, etc., taking place
comprising Fe, Cr, and Ni. The Pourbaix diagrams of such
neither at pH 11 nor at pH 14.5 in the applied potential range
alloys have been investigated by Beverskog et al. [36]. In the
[35]. Therefore, the titanium sample is very inert under the
high potential range, above þ1.4 V vs. RHE, soluble FeO2 4
applied conditions compared to stainless steel and nickel
alloy samples investigated below (Fig. 4). species might leach into solution but, more importantly,

Fig. 5 e Passive film characterization on titanium grade 2. Top. Photographs of titanium samples showing the areas that
were exposed to the electrolyte. The numbers give the ICR of the sample/GDL interface at a clamping pressure of 1.4 MPa
and the oxide thickness as obtained from the GD-OES profiles shown in the bottom.

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 international journal of hydrogen energy xxx (xxxx) xxx 7

Table 2 e Overview of ICR [mUcm2]/film thickness [nm] results obtained before and after exposure at pH 11 and 14.5 and
electrochemical experiments of all investigate materials.
Material pristine pH 11 pH 14.5
ICR film thickness ICR film thickness ICR film thickness
Titanium Grade 2 224 6 341 17 542 70
304L 239 6 415 16 602 60
316L 350 2 341 15 577 35
Nanoflex 5 8 355 16 553 16
San75 110 1 416 3 450 12
316L Coat 15 25 16 25 16 15

above þ0.8 V vs. RHE the ejection of soluble CrO2 4 is due to the mix of the various elements that Nanoflex is
confirmed by GD-OES (Fig. 6 middle and right). The current comprised of, and, therefore, considered to be outside the
densities observed in the low potential region of the CV, i.e., scope of this work.
below þ0.5 V vs. RHE, might be related to a reduction of the
oxidized species leached from solution at high potentials. Stainless-nickel grade San75
Although anodic film growth might be somewhat reversible The cyclic voltammograms of San75 in alkaline solution are
due to this, the observed behavior leads to corrosion and presented in Fig. 4. The most apparent features are two peaks
metal ion leaching into solution which, in the worst case, at þ1.27 and þ 1.39 V vs. RHE, which are absent at pH 11, the
can lead to pin-hole formation in the passive (anodic) film of sharply rising current density thereafter is, once more,
the BPP and active metal dissolution might be the result, at attributed to oxygen evolution [32]. These features can be
least short term. interpreted from the Pourbaix diagram of nickel [37] as


Stainless-steel grade 316L Ni(OH)2
4 % NiO2 þ 2H2O þ 2 e , (2)
This stainless-steel grade can also be approximated by an Fe-
Cr-Ni alloy [36] and as such has properties that are very similar which is absent below pH 13. These two features are also
to 304L described above, therefore, it is treated only very observed for a pure nickel electrode in concentrated KOH (>pH
briefly here. Fig. 4 shows that the electrochemistry of 316L is 14) at room temperature in argon-saturated solution [38]. This
very close to 304L (see above). suggests that they are a material property of nickel on the
surface and are not created by oxygen evolution/reduction.
Stainless steel-grade nanoflex
The CVs of “Nanoflex” at pH 11 and 14.5 are depicted in Fig. 4. Carbon-coated 316L (316L coat)
The onset of large current densities above þ1.4 V vs. RHE at pH Fig. 4 shows the CVs of carbon-coated 316L at pH 11 and 14.5.
14.5 can, again, be attributed to oxygen evolution per eq. (1). Oxygen evolution (see eq. (1) [32]) above þ1.4 V vs. RHE is also
Moreover, there seem to be electrochemical reactions taking observed at pH 14.5 but the current density is lower than in
place in the low potential region especially at pH 11. However, other cases, 3 mAcm2 2
geo vs. 20e40 mAcmgeo for 304L, 316L,

understanding how the Nanoflex surface interacts with the “Nanoflex”, and San75. In contrast, oxygen evolution is almost
alkaline electrolyte at elevated potentials is quite complicated absent on bulk Ti (Fig. 4).

Fig. 6 e Passive film characterization on stainless-steel grade 304L (Table 1). Top. Photographs of 304L samples showing the
areas that were exposed to the electrolyte. The numbers give the ICR of the sample/GDL interface at a clamping pressure of
1.4 MPa and the oxide thickness as obtained from the GD-OES profiles shown in the bottom.

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
8 international journal of hydrogen energy xxx (xxxx) xxx

The electrochemistry of carbon is different from the one of seems unlikely that this will keep the ICR value below the DOE
passivating metals. The oxidation of carbon is thermody- 2020 target of 10 mUcm2 for a total expected runtime of 5000 h
namically allowed above þ0.2 V vs. RHE but it is kinetically [43,44].
hindered, i.e., very slow. It becomes, however, feasible at
elevated temperature and high positive potentials of more Stainless-steel grade 304L
than þ1 V vs. RHE [19,21]. The kinetically slow oxidation of Fig. 6 and Table 2 show ICR values and the GD-OES profiles of
carbon is imagined maintaining low ICR values even during 304L samples. After exposure to sodium hydroxide solution,
failure modes (local and global hydrogen starvation) for a long interference color from oxide film growth [40] can be
time. Two types of carbon oxidation at high potential are observed. Even the pristine sample, like in the case of titanium
feasible, 1) complete oxidation, as described above (carbon grade 2 (see above), shows an Fe/Cr oxide film of 6 nm in
oxidation reaction, COR), and 2) incomplete oxidation via thickness and, thus, a high ICR of 239 mUcm2. As discussed
before, this might also lead to the absence of the initial film
C % C-O (oxygenated species). formation steps and film growth might take place directly by
the “Mott-Cabrera” mechanism, where film thickness is pro-
Complete oxidation is irreversible and removes carbon portional to potential [24]. This would be a typical case for
from the coating, on the other hand, incomplete oxidation stainless steel film growth [14]. In Fig. 6 middle and right, the
leading to alcohols, ketones, aldehydes, acids, esters, etc. samples are shown after electrochemical experiments at pH
might be reversible. It has, e.g., been found that hydroquinone 11 and 14.5, respectively. The film thickness and, in turn, the
functions on glassy carbon can be reversibly oxidized to yield ICR of the samples grows to 16 nm and 415 mUcm2 at pH 11
quinone [39]. Both types of oxidation can be observed in the and 60 nm and 602 mUcm2 at pH 14.5.
respective GD-OES profiles (Fig. 10). The GD-OES profiles in Fig. 6 middle and right (yellow
traces) show a depletion of chromium from the oxide film as
Ex-situ characterization expected from the Pourbaix diagram [36] (see above). As
explained in the “Introduction” this is a common behavior of
Titanium grade 2 passive films on stainless steels grown under alkaline condi-
Thumbnail images of the Ti samples are shown in the top part tions [14]. The thick oxide films and large ICR values that are
of Fig. 5. The brown coloration of the sample exposed to pH grown within minutes, in addition to metal ion leaching into
14.5 solution is due to interference color from the thick oxide solution (see above), make this material in its uncoated form
film [40]. An overview of obtained ICR and oxide film thick- an even worse choice for BPPs than titanium grade 2.
nesses is given in Table 2. Pristine titanium grade 2 already
shows a high ICR at the GDL/titanium interface which is owed Stainless-steel grade 316L
to its native oxide film of about 6 nm in thickness (Fig. 5) [31]. From Fig. 7 it is seen that film growth and ICR values are
This considerable oxide film thickness might lead to skipping comparable to 304L (Table 2), the typical leaching of chromium
of the early stages of film formation (see “Introduction”), for the films in alkaline solution is also observed in this case
which is (b) “nucleation and growth” [24] and, instead, jump (yellow trace in the GD-OES profiles) [14]. As in the 304L case,
right to the “high-field” or “Mott-Cabrera” mechanism [25,26]. interference color from anodic film formation can be observed
In this mechanism, also referred to as field-assisted ion sep- in the thumbnail pictures of the samples. In summary, un-
aration, the film grows linearly with applied potential at coated 316L is also not a feasible BPP material for AEMFCs.
constant pH. Since oxide or hydroxide ions must be injected
into the growing oxide/hydroxide film [24] the film becomes Stainless steel-grade nanoflex
thicker the more these ions are available, i.e., at higher pH. Fig. 8 and Table 2 present ICR values and GD-OES profiles for
Titanium dioxide is very stable under oxidizing conditions the investigated Nanoflex samples. The most striking feature
and a semiconductor with a bandgap of more than 3 eV [41] of this steel grade is the low ICR, even in the absence of
and, thus, can easily sustain large field strengths and thick pickling, i.e., the surface oxide is conductive. It is tempting to
films are expected. At pH 11 (Fig. 5 middle) already a film correlate the oxide “conductivity” to the high amount of sur-
thickness of 17 nm is obtained, which increases the ICR value face titanium (blue trace in the GD-OES profile). This is,
from the initial 224 to 341 mUcm2. PH 14.5 (Fig. 5 right) induces however, not the reason since polishing and removal of the
more severe conditions and thus a higher film thickness of surface near region also removes the high Ti content but the
about 70 nm is reached and a drastic increase in ICR to low ICR remains (not shown). Despite the low ICR in the
542 mUcm2. pristine state, it increases considerably, during electro-
Oxide (anodic) film growth has been found to be rapid with chemical experiments in alkaline solution, to the level of 304L/
most of the film thickness being established within the first 316L stainless steel grades (Figs. 6 and 7) and thick oxide films
minute of growth [27]. This means, in the best case, the anode/ causing interference color are also obtained. Furthermore, it is
cathode bipolar plate can be at þ1.5 V vs. RHE for a minute interesting to note that, in addition to chromium depletion
before detrimental ICR increase sets in and reduces the (yellow trace) [14], also titanium is depleted from the surface
effective voltage output of the cell. It has been shown by near region at pH 14.5 (Fig. 8 right). This is not unexpected
Laedre et al. [42] that, via pickling, the initial ICR value of Ti since TiO2 can be dissolved at elevated temperatures and high
grade 2 can be lowered to 5 mUcm2, this might prevent “Mott- pH values under the formation of soluble hydroxo complexes
Cabrera” type film growth for a while, since an initial oxide [45]. This type of TiO2 dissolution should also take place in
film must form via (b) “nucleation and growth” [24] but it case of bulk titanium but it is less apparent from the GD-OES

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
 international journal of hydrogen energy xxx (xxxx) xxx 9

Fig. 7 e Passive film characterization on stainless-steel grade 316L (Table 1). Top. Photographs of 316L samples showing the
areas that were exposed to the electrolyte. The numbers give the ICR of the sample/GDL interface at a clamping pressure of
140 Ncm¡2 and the oxide thickness as obtained from the GD-OES profiles shown in the bottom.

profiles (Fig. 5). In summary, Nanoflex suffers from the same Carbon-coated 316L (316L coat)
problems as 304L and 316L when it comes to its utility as BPP Fig. 10 shows coated 316L sample photos before and after
material in AEMFCs. exposure to aqueous sodium hydroxide of pH 11 and pH 14.5.
The GD-OES profiles of the pristine material and the material
Stainless-nickel grade San75 exposed to pH 11 do not differ appreciably, which shows, that
Fig. 9 and Table 2 shows that San75 suffers from similar under those conditions the carbon coating is stable and pre-
problems as all other uncoated materials presented so far, i.e., vents a change of ICR at the BPP/GDL interface. Under condi-
large ICR increase after the electrochemical experiments. In tions of pH 14.5, which is more severe in terms of carbon
addition, chromium depletion is observed here as well (yellow oxidation, the exposed area becomes transparent (Fig. 10
trace in the GD-OES profiles) [14]. In comparison to bulk Ti and right) which is a sign of thinning of the coating. This is
the stainless-steel grades the oxide films as determined by corroborated by the GD-OES depth profile. Its thickness is only
GD-OES are very thin and interference color is almost not 16 nm (complete oxidation) but also the oxygen content (black
observable. However, NiO has a wide band gap of 3.6e4 eV [46], trace) has increased (incomplete, reversible oxidation). How-
which is higher than that of TiO2, 3 eV [41], and Fe2O3, 2.1 eV ever, despite carbon oxidation, the ICR of the coated 316L re-
[47], the passive film on 304L/316L according to their Pourbaix mains almost unchanged compared to the pristine material.
diagram [36] and this, in turn, is a good indication for the low This behavior is unlike that of the uncoated materials inves-
conductivity of NiO. tigated above.

Fig. 8 e Passive film characterization on stainless-steel grade Nanoflex (Table 1). Top. Photographs of “Nanoflex” samples
showing the areas that were exposed to the electrolyte. The numbers give the ICR of the sample/GDL interface at a clamping
pressure of 1.4 MPa and the oxide thickness as obtained from the GD-OES profiles shown in the bottom.

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
10 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 9 e Passive film characterization on stainless nickel alloy San75 (Table 1). Top. Photographs of San75 samples showing
the areas that were exposed to the electrolyte. The numbers give the ICR of the sample/GDL interface at a clamping pressure
of 1.4 MPa and the oxide thickness as obtained from the GD-OES profiles shown in the bottom.

Fig. 10 e Characterization of the carbon coating on 316L, 316L Coat. Top. Photographs of 316L Coat samples showing the
areas that were exposed to the electrolyte. The numbers give the ICR of the sample/GDL interface at a clamping pressure of
1.4 MPa and the coating thickness as obtained from the GD-OES profiles is shown in the bottom.

In summary, from the tested materials only carbon-coated

316L can mitigate the drastic increase in ICR, caused by tran- Conclusions
siently high potentials of up to þ1.5 V vs. RHE during hydrogen
starvation. At drastic conditions of pH 14.5 the coating thick- The 2020 DOE target for the ICR between the bipolar plate and
ness is reduced, and oxygen functionalities are introduced but GDL is 10 mUcm2 at a clamping pressure of 1.4 MPa. The major
at pH 11 no change of the carbon coating could be detected. issue in permanently achieving this target in an operating fuel
The situation in PEMFCs would be similar for those materials cell/stack are transients which might lead to high potentials at
due to the ubiquity of transient fuel cell operation with the the bipolar plate on the cathode and anode side (>þ1.5 V vs.
exception that alkaline carbon oxidation is replaced by its RHE). These potentials are high enough to cause rapid oxide
acidic variety. (anodic) film growth on uncoated metallic bipolar plates (see

Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
 international journal of hydrogen energy xxx (xxxx) xxx 11

Table 2). This was also true when the initial oxide film was [9] Hossen MM, Artyushkova K, Atanassov P, Serov A. Synthesis
conductive (see Nanoflex). The situation can be drastically and characterization of high performing Fe-N-C catalyst for
improved by the application of a carbon coating (316L Coat) oxygen reduction reaction (ORR) in alkaline exchange
membrane fuel cells. J Power Sources 2018;375:214e21.
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[15] Serov A, Zenyuk IV, Arges CG, Chatenet M. Hot topics in
We are very thankful for the generous help of Bjo € rn Eriksson alkaline exchange membrane fuel cells. J Power Sources
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and Go€ ran Lindbergh from “Applied Electrochemistry, School of
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ion conductivity of anion-exchange membranes.
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(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122
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Please cite this article as: Proch S et al., Coated stainless steel as bipolar plate material for anion exchange membrane fuel cells
(AEMFCs), International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.04.122