materials

Article
Non-Precious Electrodes for Practical Alkaline
Water Electrolysis
Alejandro N. Colli 1,2, * , Hubert H. Girault 1 and Alberto Battistel 1
1 Laboratoire d’Electrochimie Physique et Analytique, École Polytechnique Fédérale de Lausanne, EPFL,
Valais Wallis, Rue de l’Industrie 17 Case Postale 440, CH-1951 Sion, Switzerland;
[email protected] (H.H.G.); [email protected] (A.B.)
2 Universidad Nacional del Litoral, CONICET, Programa de Electroquímica Aplicada e Ingeniería
Electroquímica (PRELINE), Facultad de Ingeniería Química, Santiago del Estero 2829, S3000AOM Santa Fe,
Argentina
* Correspondence: [email protected]




Received: 4 April 2019; Accepted: 19 April 2019; Published: 24 April 2019


Abstract: Water electrolysis is a promising approach to hydrogen production from renewable energy
sources. Alkaline water electrolyzers allow using non-noble and low-cost materials. An analysis of
common assumptions and experimental conditions (low concentrations, low temperature, low current
densities, and short-term experiments) found in the literature is reported. The steps to estimate the
reaction overpotentials for hydrogen and oxygen reactions are reported and discussed. The results of
some of the most investigated electrocatalysts, namely from the iron group elements (iron, nickel,
and cobalt) and chromium are reported. Past findings and recent progress in the development of
efficient anode and cathode materials appropriate for large-scale water electrolysis are presented. The
experimental work is done involving the direct-current electrolysis of highly concentrated potassium
hydroxide solutions at temperatures between 30 and 100 ◦ C, which are closer to industrial applications
than what is usually found in literature. Stable cell components and a good performance was achieved
using Raney nickel as a cathode and stainless steel 316L as an anode by means of a monopolar cell
at 75 ◦ C, which ran for one month at 300 mA cm−2 . Finally, the proposed catalysts showed a total
kinetic overpotential of about 550 mV at 75 ◦ C and 1 A cm−2 .

Keywords: Alkaline water electrolysis; Raney-Ni; stainless steel 316; equilibrium potential; water
splitting; iR correction

1. Introduction
Although water electrolysis has been known for around 200 years [1], this technique received
special prominence in recent years because of its potential role in the hydrogen energy economy.
However, it still contributes only a minor fraction of the total hydrogen production [2].
There are two ways to perform water electrolysis, namely, in basic or acidic medium, the latter
is made possible by a polymeric membrane (in general Nafion), which acts also as solid electrolyte.
Electrolyzers based on this technology offer major advantages over their alkaline counterparts such as
greater safety through the absence of a caustic electrolyte, a more compact design due to higher current
densities, and higher operating differential pressures. The limited lifetime and the high cost of the
membranes and cell components, usually titanium plating to resist corrosion under acidic medium, are
important limitations for this technology, as also is the use of expensive precious metal electrocatalysts.
Recently it has been shown with a simple physical model, parameterized with experimental data and
based on the gas-permeation voltage–current characteristic, and heat balances that alkaline cells could
achieve better efficiency than cells with Nafion membranes [3].

Materials 2019, 12, 1336; doi:10.3390/ma12081336 www.mdpi.com/journal/materials

Materials 2019, 12, 1336 2 of 17

Operation in alkaline conditions also unlocks the possibility of using non-precious metal
electrocatalysts [4], cheaper cell components, and lower energy consumption, leading to the possibility
of cheaper hydrogen production. Existing alkaline water electrolysis plants are based on cells with an
aqueous KOH or NaOH (20–40 wt.%) electrolyte and a porous separator at temperatures between 70
and 110 ◦ C and at atmospheric or elevated pressure (up to 30 bar) [1]. The cell and stack costs represent
nearly 20%–30% of the total cost of an alkaline electrolyzer. This means that an increase in the cell
performances is well sought as long it is balanced by a small cost increase, which favors non-precious
metal materials in commercial water electrolysis cells.
Electrode materials should have good corrosion resistance, high conductivity, and high catalytic
activity for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Besides
the catalyst composition, the morphology has a strong influence on both HER and OER, being less
important for OER. Polarization curves are the key performance indicators used to evaluate and
compare the performances of catalysts for HER and OER; however, polarization curves can differ
significantly from one author to another. The literature can be a poor guide to the performance
of cathodes and/or anodes for industrial water electrolyzers. Comparisons based on published
performance is difficult to do because: (i) much of the literature relates to room temperature and
pressure; (ii) the equilibrium potential is not corrected for temperature and strong alkali concentrations,
leading to disparity between different authors that use different temperatures and concentrations of
supporting electrolytes; (iii) the geometrical area of electrodes when electrode meshes are used; (iv)
unclear effect of bubble coverage or iR compensation [5]; (v) most of the experiments in the literature
are performed at low current densities [6]; and finally and most importantly (vi) the discussion of HER
and OER in terms of Tafel slopes and exchange current densities measured in current density ranges
far below those employed for industrial water electrolysis. Moreover, it is important to test electrode
materials under realistic process conditions for an extended period of time [7].
Another research branch aims at optimizing cell designs to provide high surface areas for
catalysts, low cell resistance, proper flow design for the evacuation of gasses, and appropriate current
and potential distribution [8,9]. Configuration of water electrolysis cells can go from conventional
monopolar tank cells (simple, reliable, and flexible) through bipolar filter press cells (lower ohmic
losses and more compact) and finally to the zero-gap design.
In the first part of the present contribution we intend to give guideline for people working in the
field about common assumptions usually made that can produce errors in results and confuse readers.
Additionally, we report our investigations and various comparisons on some of the most promising
electrocatalysts for HER and OER for alkaline electrolyzers found in literature, with the focus on their
applications in real industrial devices.

2. Materials and Methods

2.1. Common Assumptions

2.1.1. Equilibrium Potential

Although one might think that the calculation of the values of the relevant thermodynamics
parameters for various operating condition would be a relatively straightforward matter, serious errors
have crept into the literature and have led to a considerable amount of confusion. In contrast to most
activity coefficients of uncharged species, salt activity coefficients can significantly differ from unity. As
a result, they must be always carefully considered to make proper calculations whenever the chemical
potential of an electrolyte in solution is involved.
In the following development it was assumed that there were two distinct compartments, one
for hydrogen and one for oxygen evolution, at atmospheric or the same pressure, p, as it was usually
done in an alkaline electrolyzer through the use of matched pressure relief valves. In each of these
compartments, the gaseous solutions were in equilibrium with water in the electrolyte. Also, hydrogen,
oxygen, and water vapor were considered as ideal gases, and the first two formed ideal binary gaseous
Materials 2019, 12, 1336 3 of 17

solutions with the third. The partial pressure of water vapor in each of the wet gases will be equal to
pw , the aqueous vapor pressure of the KOH/NaOH solution:

p = pw + pH2 = pw + pO2 , (1)

Starting from the equations of alkaline water electrolysis:

Anode 2 OH−
1/2O2 + H2 O + 2e− , (2)

Cathode 2 H2 O + 2e−
H2 + 2 OH− , (3)

Total H2 O
H2 + 1/2 O2 , (4)

and considering the definition of equilibrium potential for each half reaction, then:

aH2 O fO1/2
!
RT
From Equation (2) E+ = E0H O/O + ln 2
, (5)
2 2 2F a2
OH−

!
a2 f
RT OH− H2
From Equation (3) E− = E0H O/H − ln , (6)
2 2 2F a2H O
2

fH2 fO1/2
!
RT
From Equation (4) E+ − E− = E0H − E0H + 2F ln aH2 O
2
, (7)
2 O/O2 2 O/H2

where E0 is the standard half-cell potential and can be obtained from thermodynamic tables, R is the
universal gas constant, F the Faraday constant, T the temperature, ai the activity of the ith specie, and
f i the fugacity of the ith gaseous specie. The activity, ai , of a given specie can be expressed by: ai = mi γi ,
where m is molality (or molarity) and γ the activity coefficient.
In order to predict the activity coefficients of strong electrolytes in pure solutions we used the
methodology proposed by Kusik and Meissner [10], as it was already shown to be accurate [8,11]. As
we considered an ideal gas (experiments are usually done at atmospheric pressure), fugacity can be
replaced by the partial pressure of the gases.
Figure 1 part (a) shows the equilibrium potential correction at a given temperature that should
be applied to the standard conditions when experiments are done under different ionic forces. It
can be observed that for ionic strength higher than one, the correction potential from the standard
conditions was larger for Equation (6) than for Equation (5), and the difference increased according to
the ionic strength. This behavior can be explained taking into account the activity coefficients and
water activity. The higher the concentration of KOH/NaOH, the lower the water activity was, and the
more Equation (6) and Equation (5) departed from the standard. Also, a higher equilibrium potential
for the full reaction, Equation (4), could be observed from Equation (7). Thus, with an increasing
the KOH/NaOH concentration, water activity was decreased, viz., a larger voltage was required.
However, in practical applications this is a small price to pay to keep the electrolyte resistance as
low as possible. In real-world usage, with an electrolyte concentration of about 30% wt. (~7 M), the
equilibrium potentials for both the HER and the OER would shift negatively from about 70–90 mV at
room temperature. Nevertheless, the voltage to split water would be increased by only 10 mV.
Some authors have shown [12] that hydrogen overpotential is higher than oxygen overpotential,
which is somewhat difficult to accept given the fast kinetics for hydrogen evolution and the slow
kinetics for oxygen [13]. One of the possible explanations can be the shifting in equilibrium potential
due to actual activity coefficients, as explained above.
 fi the fugacity of the ith gaseous specie. The activity, ai, of a given specie can be expressed by: ai = miγi,
where m is molality (or molarity) and γ the activity coefficient.
In order to predict the activity coefficients of strong electrolytes in pure solutions we used the
methodology proposed by Kusik and Meissner [10], as it was already shown to be accurate [8,11]. As
we considered
Materials 2019, 12, 1336an ideal gas (experiments are usually done at atmospheric pressure), fugacity can
4 of 17 be
replaced by the partial pressure of the gases.
0.65
Correction Potential / V 0.20 0.60
0.15 O2 25°C 0.55
H2 25°C 0.50
0.10

Ε (vs. SHE)
O2 100°C 0.45 Silver/Silver-Cloride
0.05 H2 100°C 0.40 Calomel
Mercury/Mercury(II)-Oxide
0.00 0.35
Mercury/Mercury(I)-Sulfate
0.30
-0.05 0.25
-0.10 0.20
0.15
-0.15 0.10
-0.20 0.05
0.00
-0.25
0 2 4 6 8 10 12 20 30 40 50 60 70 80 90 100
Ionic Strength Τ (°C)
(a) (b)
Figure
Figure 1. Correction
1. (a) (a) Correction
of theofequilibrium
the equilibrium potential
potential from standard
from standard conditions
conditions vs. ionicvs. ionic strength
strength of KOH. of
T = KOH.
25 andT100 P = 1100
◦ C;and
= 25 °C;(b)
atm.; P =Potential
1 atm.; vs.
(b) SHE
Potential vs. SHE
for different for different
reference reference
electrodes electrodes
against against
temperature.
temperature.
Figure 1 part (b) shows the potential correction vs. the standard hydrogen electrode (SHE) for
differentFigure
common reference
1 part electrodes
(a) shows as a function
the equilibrium of temperature.
potential correction Additionally, care must that
at a given temperature be taken
should
with
beregards
appliedtotoliquid junctionconditions
the standard potentials when
(LJPs),experiments
which depends on the
are done reference
under electrode
different ionic used forItacan
forces.
given
be electrolyte.
observed thatChanges in LJPs
for ionic can behigher
strength fairly large,
than especially under the dilution
one, the correction potentialconditions
from theused to
standard
determine relative ion permeabilities. Corrections up to 55 mV can be necessary [14].
In the present contribution, the actual potentials were corrected for temperature [15], LJP [16],
equilibrium potential [10], and reference electrode potential as well (from Figure 1 part (b)).

2.1.2. iR Correction
In order to investigate the kinetics of an electrochemical reaction, any other source of uncertainty
should be reduced. In particular, the ohmic drop, which is the voltage drop due to the resistance of
the solution or due to the electrical contacts, is one of the major sources of disturbance. It distorts the
cyclic voltammetry and flattens the polarization curves.
One common misconception is that by knowing the ohmic drop, it is possible to correct cyclic
voltammetry simply by adding to the potential scale a value taken by multiplying the current and the
ohmic drop. This is, in general, a good way for steady-state, or quasi-steady-state techniques such as
staircase voltammetries or when the current is directly controlled, e.g., galvanodynamic experiments.
In a dynamic experiment like cyclic voltammetry, the effect of the ohmic drop is more subtle: it alters
the real scan rate perceived by the electrode interface [17] and a more mathematical involved solution
is necessary. Alternatively, if the instrument at hand allows it, the use of an uncompensated resistance
correction directly during the experiment is advisable.
There are two possibilities to measure the ohmic drop: electrochemical impedance spectroscopy
(EIS) and current-interrupt experiments. The first relies on the measurement of the impedance of
the electrochemical cell at different frequencies and estimating the ohmic drop as the high frequency
intercept of the impedance in the complex plane with the real axis. For a system to be well-conditioned,
the impedance should tend toward a real value at high frequency, and it is usually a straightforward
method to determine this value. On the other hand, in a current-interrupt measurement the current in
the cell is switched off briefly, and the voltage is recorded a few microseconds after the interruption.
Both methodologies have their drawbacks, primary EIS require additional circuitry, which is not
always included in commercially available potentiostats, while current-interrupt heavily relies on an
elevated time resolution required to be able to resolve the current at the exact time of the switching.
An example of a simple Randles circuit with a constant phase element (CPE) in place of a standard
capacitor is depicted in Figure 2. Part (a) shows the Nyquist plot, part (b) shows the current decay for
 estimate of the ohmic drop of 10% in the case of α = 1 and of 50% in the case of α = 0.8. The parameter
α is usually related to the surface roughness of the electrode [18] and current distribution in the cell
[19].
Additionally, from Figure 2 part (c) it can be seen how the error in estimating the cell resistance,
by the current-interrupt method, increases while the measuring time delay and the kinetic resistance
Materials 12, 1336
2019, This
increases. last phenomenon is more important for OER because of the slow reaction 5rate. of 17

Therefore, extrapolation of ohmic drop from current-interrupting should be made with extreme care.
In our experiments the ohmic drop extracted by EIS and current-interrupted was within a 5%–
a profile of potential when the cell is switched on (Inset), and part (c) depicts the errors of estimating
15% difference when measured in correspondence with HER, but it gave much larger differences
the cell resistance, R1 , as a function of the kinetic resistance, R2 , by the current-interrupt method.
when measured in correspondence with OER (nearly 50%–70%).
600
α = 1.00 1.0
0.010 80 R1 = 10 Ω
500 251 Hz α = 0.95
0.8 R1 = 50 Ω
α = 0.90

400
α = 0.85 0.008 0.6 α = 1.00 R1 = 100 Ω

U/V
α = 0.95 60 R1 = 500 Ω
-ZIm / Ω

Error / %
0.4 α = 0.90

Ι/Α
300 0.006 α = 0.85
1000 Hz 0.2

200 0.004 0.0

40
100 Hz
0.0 200.0? 400.0?
100 t/s
0.002
20
0
0.000
-100 0
0 200 400 600 800 1000 1200 0.0 100.0? 200.0? 300.0? 400.0? 500.0? 1 10 100
ZRe / Ω t/s R2 / Ω
(a) (b) (c)
Figure2.2. (a) Nyquist
Figure Nyquistplot
plotofofa atypical
typicalRandles circuit
Randles made
circuit withwith
made R1 =Ω,100
R1 = 100 R2 =Ω,
1000 = and
R2 Ω, 1000a Ω,
constant
and a
phase element
constant (CPE) with
phase element Q = 10
(CPE) with Q = 10−6 S sα .of(b)
–6 S sα. (b) Profiles theProfiles
currentofgiven by the potential
the current given bystep
theand inset:
potential
1V and
step potential
inset:step used to simulate
1V potential step used a current-interrupted experiment. (c)experiment.
to simulate a current-interrupted Error (%) of (c)
estimating
Error (%)the
of
cell resistance
estimating the cell ) by the current-interrupt
(R1resistance method. Q = 10
(R1 ) by the current-interrupt method. Q = 10−6 S sα , α = 1.done
–6 S sα, α = 1. Measurement every 10
Measurement
μs (dashed
done every 10 lines) or 50 μslines)
µs (dashed (full lines).
or 50 µs (full lines).

The high frequency intercept was clearly visible in the Nyquist plot (Figure 2 part (a)) independently
3. Experiment
of the constant phase element. However, the slope of the current decay in part (b) was influenced by
3.1.α Electrode
the value of Materials
the CPE: and Synthesis
the lower the value the higher the slope. In this particular case an uncertainty
of 10 µs in reading
Nickel the stainless
(Ni) and exact time of the
steel 316Lswitching
(SS316L)would produce an
disk electrodes oferror
3 mmindiameter
the estimatewereofbuilt
the ohmic
from
drop of 10% in the case of α = 1 and of 50% in the case of α = 0.8. The parameter
commercially available nickel 99.78% from ADVENT research materials and stainless steel 316L α is usually related
fromto
the surface roughness of the electrode [18] and current distribution in the
Shanghai Bozhong Metal Group, respectively. The electrodes were polished with sandpaper (#300– cell [19].
Additionally,
#1500) from Figure
without significant 2 part (c)init the
differences canobtained
be seen how the for
results error
theindifferent
estimating the cell resistance,
roughness. Aged Ni
by the current-interrupt method, increases while the measuring
was obtained by putting the Ni electrode surface in contact with 6–7 M KOH/NaOH time delay and the kinetic
andresistance
working
increases.
few hoursThis last phenomenon
as anode is more(HER)
(OER) or cathode important for OER
at a fixed because
current of the
density slow reaction
(usually >200 mA rate.
cmTherefore,
–2).

extrapolation of ohmic
In the case of Raneydropnickel
from current-interrupting
on Ni-Zn base (Ra-Ni), should be made
we have with extreme
performed care. from a
electroplating
In our experiments the ohmic drop extracted by EIS and current-interrupted
modified Watts bath (360 g/L of nickel(II) sulfate hexa/hepta-hydrate for plating, 30 g/L of zinc was within a 5%–15%
sulfate
difference
heptahydrate when99.5%
measured in correspondence
from Aldrich, and 40 g/Lwith HER,
of boric but99%
acid it gave
from much
AB) larger
onto Cu differences
substrate.when
The
measured
materialsin correspondence
were withdeposited
galvanostatically OER (nearly at a 50%–70%).
current density of –50 mA cm–2 at 55 °C and facing up
without stirring during 90 min. After deposition the electrodes were treated for some hours in 6 M
3. Experiment
KOH solution at room temperature. During this time the electrodes produced hydrogen making the
solution sparkling. Several materials were synthetized and tested for HER and OER. Apart Raney
3.1. Electrode Materials and Synthesis
nickel (Ra-Ni), also nickel, copper, and cobalt alloys (NiCuCo) were electroplated from a modified
Nickel
Watts bath (Ni)
withand
360 stainless steel(II)
g/L of nickel 316L (SS316L)
sulfate disk electrodesfor
hexa/hepta-hydrate ofplating
3 mm diameter were
( >20.6% Ni andbuilt from
Co basis
commercially
from Aldrich),available
30 g/L ofnickel 99.78%
zinc sulfate from ADVENT
heptahydrate research
(99.5% materials
from Aldrich), andofstainless
20 g/L steel
Copper(II) 316L
sulfate
from Shanghai Bozhong Metal Group, respectively. The electrodes were polished
pentahydrate (>98% from Aldrich), and 40 g/L of boric acid (>99.5% from Aldrich) onto a Cu with sandpaper
(#300–#1500)
substrate. without significant differences in the obtained results for the different roughness. Aged
Ni was obtained by putting the Ni electrode surface in contact with 6–7 M KOH/NaOH and working
few hours as anode (OER) or cathode (HER) at a fixed current density (usually >200 mA cm−2 ).
In the case of Raney nickel on Ni-Zn base (Ra-Ni), we have performed electroplating from a
modified Watts bath (360 g/L of nickel(II) sulfate hexa/hepta-hydrate for plating, 30 g/L of zinc sulfate
heptahydrate 99.5% from Aldrich, and 40 g/L of boric acid 99% from AB) onto Cu substrate. The
materials were galvanostatically deposited at a current density of –50 mA cm−2 at 55 ◦ C and facing up
without stirring during 90 min. After deposition the electrodes were treated for some hours in 6 M
KOH solution at room temperature. During this time the electrodes produced hydrogen making the
solution sparkling. Several materials were synthetized and tested for HER and OER. Apart Raney
nickel (Ra-Ni), also nickel, copper, and cobalt alloys (NiCuCo) were electroplated from a modified
Watts bath with 360 g/L of nickel (II) sulfate hexa/hepta-hydrate for plating ( >20.6% Ni and Co basis
Materials 2019, 12, 1336 6 of 17

from Aldrich),
Materials 30 xg/L
2019, 12, FORofPEER
zincREVIEW
sulfate heptahydrate (99.5% from Aldrich), 20 g/L of Copper(II) sulfate 6 of 16
pentahydrate (>98% from Aldrich), and 40 g/L of boric acid (>99.5% from Aldrich) onto a Cu substrate.
Additionally,
Additionally, porous
porous nickel
nickel [20,21],
[20,21], Co,Co, NiFe
NiFe [22],
[22], andand Ni-Fe(OH)
Ni-Fe(OH) [23,24]
[23,24] were
were synthesized
synthesized
following
following thethe given
given references.
references. Also,
Also, addition
addition of Co
of Co in solution
in solution through
through dissolution
dissolution of some
of some traces
traces of of
CoSOCoSO
4 4 (Co
(Co in in situ)
situ) waswas tried.
tried.

3.2.3.2.
Electrolysis CellCell
Electrolysis Assembly
Assembly
TheThe
cellcell
waswas mademadeof two pieces
of two of polypropylene
pieces of polypropylene (one is shown
(one in Figure
is shown 3) with3)a with
in Figure Zirfon Perl 500Perl
a Zirfon
UTP (AGFA) membrane in between. The electrode area was 3.14 2
500 UTP (AGFA) membrane in between. The electrode areacmwasand3.14had
cma 10
2 andmmhadinter-electrode
a 10 mm inter-
gapelectrode
to allow easy
gap flow of electrolyte
to allow easy flow andofgasses. The reactor
electrolyte was part
and gasses. Theofreactor
a flow circuit system
was part of aconsisting
flow circuit
of asystem
peristaltic multichannel
consisting Ismatec® pump,
of a peristaltic a reservoir,
multichannel and connections
Ismatec ® pump, a to maintainand
reservoir, the temperature
connections to
at the preset value,
maintain 75 ◦ C. The electrolyte
the temperature at the presetwasvalue,
pumped 75 from a single
°C. The reservoir
electrolyte wasof pumped
500 mL through
from atwosingle
channels to the
reservoir cell,mL
of 500 and the outlet
through two of both channels
channels was
to the cell, returned
and to the
the outlet samechannels
of both reservoir,
waswhere the to
returned
solution was reservoir,
the same purged with nitrogen.
where The flow
the solution rate
was was increased
purged until no
with nitrogen. improvement
The flow rate waswasincreased
read in theuntil
cellno
voltage (U cell ), being the final operational flow −1
improvement was read in the cell voltage (Urate around
cell), being 250
the mLoperational
final min . flow rate around 250
mL min–1.

Figure
Figure 3. Schematic
3. Schematic representation
representation of one
of one halfhalf of the
of the cell.cell.
(1) (1) Electrode
Electrode housing.
housing. (2) (2) Structural
Structural divider.
divider.
(3) Membrane.
(3) Membrane.(4) Electrolyte inletinlet
(4) Electrolyte port. (5) (5)
port. Electrolyte outlet
Electrolyte port.
outlet port.

3.3.3.3.
Electrochemical Measurements
Electrochemical Measurements
TheThe
electrochemical experiments were were
conducted with a with
BioLogic ® SP-150 potentiostat (Bio-Logic
electrochemical experiments conducted a BioLogic ® SP-150 potentiostat (Bio-
Science Instruments SAS, Seyssinet-Pariset, France) for the EIS, current-interrupted
Logic Science Instruments SAS, Seyssinet-Pariset, France) for the EIS, current-interrupted experiments,
andexperiments,
the polarizations
and thewith a two-channel
polarizations with power supply power
a two-channel for thesupply
long-term experiments.
for the In all the
long-term experiments.
experiments, the reference electrode was an Ag|AgCl| 3 M KCl with a double-junction
In all the experiments, the reference electrode was an Ag|AgCl| 3 M KCl with a double-junction filled with the
same electrolyte −
filled with theof the main
same solution
electrolyte (6 M
of the mainKOH) to avoid
solution (6 MClKOH)contaminations. For the polarization
to avoid Cl– contaminations. For the
experiments, N 2 bubbling and vigorous stirring were used to avoid bubble
polarization experiments, N2 bubbling and vigorous stirring were used to avoid bubble coverage andcoverage
to ensureand
thattothe reaction
ensure that rate was notrate
the reaction limited
was bynotthe mass-transfer
limited (agitation was
by the mass-transfer increased
(agitation wasuntil no change
increased until no
in potential was found). The ohmic resistance was measured for each
change in potential was found). The ohmic resistance was measured for each experiment byexperiment by impedance
spectroscopy,
impedanceestimated by the
spectroscopy, interceptby
estimated of the
the intercept
high frequency
of the arc
highwith the realarc
frequency axis, iR real
andthe
with correction
axis, and
wasiRemployed to eliminate its effect from the results. Finally, the equilibrium potentials
correction was employed to eliminate its effect from the results. Finally, the equilibrium in thepotentials
given
conditions wereconditions
in the given calculatedwere
by using the activity
calculated coefficients
by using given
the activity by Kusik and
coefficients givenMeissner
by Kusik [10],
andand the
Meissner
[10], and the respective overpotentials were derived as described in Section 2.1. All experiments were
performed at temperatures between 30 and 100 °C in 6 M KOH with a platinum counter electrode.
Two kinds of experiments were performed. The first was a current-controlled polarization
where the current was held constant. Once the sample reached steady-state (between 5 and 15 min),
Materials 2019, 12, 1336 7 of 17

respective overpotentials were derived as described in Section 2.1. All experiments were performed at
temperatures between 30 and 100 ◦ C in 6 M KOH with a platinum counter electrode.
Two kinds of experiments were performed. The first was a current-controlled polarization where
the current was held constant. Once the sample reached steady-state (between 5 and 15 min), the
value of the potential vs. the reference was taken. Subsequent current steps were done for the same
sample between 5 and 1000 mA cm−2 . The second kind of experiment was a long-term polarization at
300 mA cm−2 at a constant temperature in the electrolysis cell.

4. Results and Discussion

4.1. Kinetic Behavior

Comparison of the catalyst based on the published performance was difficult, as detailed data on
measuring techniques are not given, or various techniques were applied. Operation conditions, such as
the temperature, often differed vastly, and different types and concentrations of electrolytes were used.
One of the problems observed with Ni-based materials for water electrolysis was the loss of
activity, as indicated by the time variation of the cathode and anode potentials [13]. Thus, instead of
a classical quasi-steady-state linear sweep voltammetry, the working electrode was held at a given
current density until steady-state was reached. The potentials of the working and counter electrode
were monitored against the Ag|AgCl| 3 M KCl reference electrode. The same experiments were then
performed at different temperatures for different materials. All the overpotentials were corrected for
the shift of potential of the reference electrode and of the equilibrium potential because there were
changes in temperature and electrolyte concentrations as well as an iR drop.

4.1.1. Hydrogen Evolution Reaction (HER)

Ni-based alloys have been the object of extensive research efforts. Considering pure metals, Ni is
the most active non-noble metal [25]. Raney nickel was introduced in the fifties as alkaline fuel cell
anodes and has been used for almost 50 years as an effective electrocataliyst for cathodic hydrogen
evolution [6,26]. Raney nickel is a highly porous nickel with a high internal surface area. It is obtained
by alloying nickel with zinc, in which case it is also known under the name of Urushibara nickel. It
can also be made out of nickel and aluminum or silicon. Zn, Al, or Si are then leached out to leave a
very porous and active material. After leaching, the porous nickel coating contains hydrogen in an
adsorbed state or as a nickel hydride. Therefore, it is indispensable to oxidize this hydrogen under
controlled potential to obtain the activated Ra-Ni coating [27].
Polarization curves from a nickel disk electrode of 3 mm diameter were obtained, as shown
in Figure 4, by working at different current densities. Raney nickel was synthesized, as described
in Section 3.1, and characterized electrochemically for HER in 6 M KOH, proving its significant
catalytic properties.
Figure 4a shows the HER for bare nickel (Ni), cobalt (Co), and copper (Cu), nickel-copper-cobalt
alloy (NiCuCo), Raney nickel (Ra-Ni), and SS316L at 30 ◦ C. In Figure 4b the overpotentials for aged
bare Ni and Ra-Ni at different temperatures are also shown. If we compared Ra-Ni with Ni it could be
seen that at 75 ◦ C and at 400 mA cm−2 it was possible to reduce the cell potential by almost 300 mV.
Several other materials were taken in consideration for comparison, but not directly tested:
Ni dendrites [28]; Ni-rare earth alloys [29]; NiCu compact, porous [30,31], metallurgical, and
dealloyed [32–38]; Ni-Co-W [39]; NiCuZnB [40] smooth [22,31,41,42] and porous [43–46]; NiCo
by electroless-plating deposition [47]; Ni-Co [41,43,45]; Ni-Fe [22]; in situ activation of Ni-Co with
Mo [48]; electrodeposited Ni-Co-Mo; NiMo [49]; NiCoZn alloys [50–52]; Raney-Co [44]; Ni-Mo [53];
nonporous cauliflower-like cobalt-nickel hydroxide (CoNi) [54]; and black nickel (Ni-S) [12]. However,
since their results were worse than the materials tested in this work, and the conditions of the
experiments were too different from our experiments (low electrolyte concentration or uncertain
equilibrium potential correction), only some of their results were summarized in Tables 1–3. As found
Materials 2019, 12, 1336 8 of 17

also by other authors [21,50,55–59], Ra-Ni showed the best performances. Nevertheless, there is still
active research on cathodic materials and their synthesis, as it is perceived that improvements are still
possible in order to provide lower overpotentials and cheaper catalysts [60].

(a) (b)

Figure 4. (a) Polarization curves for several catalysts for HER at 30 ◦ C (Ni was not aged). (b) Comparison
of aged Ni and Ra–Ni between 30 and 100 ◦ C.

Table 1. Summary of NiCu alloys found in literature for HER in alkaline conditions.

Compact Compact Sintered

Dense Metallurgical NiCuZn
and Porous and Porous NiCu [34] Porous
NiCu [35] NiCu [36] [40]
NiCu [32] NiCu [33] Ni-Cu [35]
j (mA/cm2 ) Overpotential (mV)
100 −410 −307 −370 −500 −400 −300 −210
200 −620 −560 −460 −650 −550 – –
T (◦ C) room room room 35 35 25 room
KOH conc. 1M 1M 6M 6M 6M 6 M NaOH 1M

Table 2. Summary of NiCo alloys found in literature for HER in alkaline conditions.

Porous
Smooth Smooth Smooth NiCo Porous Raney NiCoZn NiCoZn
NiCo
NiCo [22] NiCo [41] NiCo [31] [42] Ni-Co [43] Co [44] [50] [51]
(a) [45,46]
(b)
j (mA/cm2 ) Overpotential (mV)
100 −380 −480 −380 −430 −350 −410 −165 −125 −230
200 - - - - - −450 −210 −145 −370
T (◦ C) 25 room 50 25 room 80 30 25 room
KOH conc. 6M 0.5 M 30% 6M 30% 3M 30% 0.5M NaOH 1M

Table 3. Best alloys for HER found in the literature.

Ra–Ni
Ni- Porous Ni2 PW12 Ni-Porous Ra–Ni [30] Ra–Ni [57]
[55,62] from
[31] [44] [61] from Al from Zn
Al and Ti
j (mA/cm2 ) Overpotential (mV)
100 −300 −300 −150 −115 −110 −110
200 – −365 −190 −170 −160 −150
T (◦ C) 50 80 30 22 30 50
KOH conc. 30% 3M 30% 6M 1M 30%
Materials 2019, 12, 1336 9 of 17

It can be concluded that alloying Ni with, for example, Co or/and Cu, resulted in an increased
electrocatalytic activity in the HER when comparing with pure Ni, Cu, and Co. This was due to
an improved intrinsic activity of the materials. However, Co or/and Cu-modification of type Raney
Ni-based electrodes did not improve the apparent catalytic activity of these materials as compared to
Ra-Ni. Nevertheless, it was difficult to assert whether the increase in the intrinsic activity compensated
for the lower cathode surface area [57], which was one of the key features of Raney nickel.
Finally, it is important to point out that our results coincided with the ones obtained by Kjartandóttir
et al. [63] for polished Ni 99% and Raney nickel obtained by physical vapor deposition or by vacuum
plasma spraying [64]. It was noteworthy that Ni required an aging/activation process of some 12 h
in concentrated KOH (6 M) before performing at its best. All the materials used in this study were
systematically pretreated in concentrated solution before use. Without ageing, Ni behavior for HER
and OER can vary up to 15% in the final overpotential. This variation can, in our opinion, explain most
of the discrepancy found in in literature.

4.1.2. Oxygen Evolution Reaction (OER)

The irreversibility of the oxygen electrode reaction is the main cause of efficiency losses in water
electrolysis cells. It is of interest to note, as previous researchers pointed out, that, as opposed to
HER, there is little difference in the polarization behavior of smooth and porous structures during O2
evolution. This is mainly due to ineffective utilization of the internal surface area of the porous body
as the surface is blocked by bigger gas bubbles involved in O2 evolution [65].
As in the case of the HER cathodes, some anode materials exhibited performance variation with
time. Figure 5, part (a) shows the polarization curves for Co in situ [47] and porous Ni, and they
have been compared with bare Ni. We have synthetized Ni-Fe(OH) as described elsewhere [23,24],
and found overpotentials as described by Dionigi and Strasser [66] at low temperatures (blue line
in Figure 5a). However, we found instability at high current density, high temperature, and KOH
concentration after 16 h of experiment. Hydrotalcite-wrapped Co–B alloy [67] was proposed and
tested at a low current density and low OH− concentration. Also, mixed oxides were investigated as
electrocatalysts for OER (Fe, Co, Mo). However, due to instability or no practical gain with regards to
Ni, they have been discarded. Iron impurities in thin film nickel oxides have shown good behavior in
comparison with bare Ni [68], unless such low overpotentials were anomalous and could be explained
by a non-proper equilibrium potential for 5.5 M KOH, as was described in Section 2.1. Hierarchically
(a)
structured three-dimensional nickel–iron electrodes were suggested [69],(b)but they did differ with
regards to aged Ni if the proper equilibrium potential was used for 10 M KOH.

(a) (b)
Figure 5. Polarization curves for the oxygen evolution reaction (OER) at (a) 30 ◦ C and (b) between 30
and 100 ◦ C.
Materials 2019, 12, 1336 10 of 17

Recently, it has been pointed out that commercially available stainless steel (SS) 316L can be an
efficient electrocatalyst for water oxidation in alkaline solution [70]. Our results with SS316L were
in agreement with in situ growth of Fe(Ni)OOH on stainless steel [71], first row transition metal
(oxy)hydroxides [72], aged SS [73], or SS AISI 304 oxidized by exposure to Cl2 [74]. They are shown in
Figure 5a for
Materials 2019, ◦ Cx and
3012, FOR Figure 5b for the range 30–100 ◦ C.
PEER REVIEW 10 of 16
With regards to other catalysts from the literature, Co3 O4 could save around 30 mV (at 400 mA cm−2
and 25 ◦Recently, it has been
C) in comparison withpointed out that
bare nickel commercially
metal [7]. However, available stainless
it seems that itsteel (SS) 316Latcan
deactivates highbe an
efficient electrocatalyst
temperature [27], and recent forstudies
water oxidation
[75–78] did in not
alkaline
showsolution [70]. Our results
better performance thanwithagedSS316L were in
SS304 [73].
agreement with in situ growth of Fe(Ni)OOH on stainless steel [71],
Our results agreed with the ones obtained by Kjartandóttir et al. [63] for polished Ni 99% and also with first row transition metal
the (oxy)hydroxides
ones of Wendt [79] [72],
foraged
smooth SS [73],
Ni. or SS AISI 304 oxidized by exposure to Cl2 [74]. They are shown
inTaking
Figureinto 5a for 30 °C and
account HER and OER Figure 5bresults,
for the itrange 30–100 °C.
is important to point out that the present results were
With regards to other catalysts from the
in agreement with those presented also by others [27,62,64] and literature, Co3O 4 could save around 30 mV (at 400 mA
show that OER overpotentials can be
twicecmas and
–2
large25 as°C) in comparison
those for HER [7,80]. withAsbare nickel metal
mentioned [7]. However,
by Pletcher and Li in it seems that
2011 [6], it deactivates
a cell at high
voltage target
lower than 2 V at a current density of 1 A cm for a cell operating below 100 C is already realized. In[73].
temperature [27], and recent studies [75–78]
−2 did not show better performance
◦ than aged SS304
ourOurcase,results agreed with
extrapolating from the ones4b
Figures obtained
and 5b, by Kjartandóttir
a cell comprised et of al. [63] nickel
Raney for polished Ni 99%would
and SS1316L and also
show with the ones
a total kineticof overpotential
Wendt [79] forofsmooth
about 550Ni. mV at 75 ◦ C and 1 A cm−2 .
Taking into account HER and OER results, it is important to point out that the present results
4.2. were
Long in Term Experiments
agreement withand Cellpresented
those Behavior also by others [27,62,64] and show that OER overpotentials
can be twice as large as those for HER [7,80]. As mentioned by Pletcher and Li in 2011 [6], a cell
The long-term performance of a catalyst is essential for technical applications. To be able to
voltage target lower than 2 V at a current density of 1 A cm–2 for a cell operating below 100 °C is
evaluate the ageing rate of the catalyst, galvanostatic long-term experiments were carried out. In
already realized. In our case, extrapolating from Figure 4b and 5b, a cell comprised of Raney nickel
accordance with the operating conditions of commercial water electrolyzers, the electrodes were tested
and SS1316L would show a total kinetic overpotential of about 550 mV at 75 °C and 1 A cm–2.
at a constant current density of 300 mA cm−2 in 6 M KOH at 75 ◦ C.
Two run tests were performed: one with nickel in both electrodes (Ni–Ni) and the other one with
4.2. Long Term Experiments and Cell Behavior
SS316L on the anode and Raney nickel on the cathode (SS316L–Ra–Ni).
From The long-term
Figure 6 it can performance
be seen thatof a catalyst
initially, is essential
the Ni–Ni for about
cell had technical
a 250applications.
mV larger cell Tovoltage
be able to
thanevaluate the ageing
SS316L–Ra–Ni. Thisratedifference
of the catalyst,
grew togalvanostatic
650 mV at the long-term
25th day.experiments
The better were carried out.
performances of In
accordance were
SS316L–Ra–Ni with mainly
the operating
due to aconditions
better HER, ofascommercial
can be seenwater electrolyzers,
from Figures 4 and 5. theThe
electrodes were
voltage of
tested at a constant current density of 300 mA cm –2 in 6 M KOH at 75 °C.
SS316L–Ra–Ni oscillated around 0.05 V for 30 d without giving any sign of losses during that period.
Two run
Ni–Ni instead, tests were
constantly performed:with
deteriorated one with
time.nickel in both electrodes (Ni–Ni) and the other one with
SS316L on the anode and Raney nickel on the cathode (SS316L–Ra–Ni).
3.0

2.5

2.0
Ucell / V

1.5

1.0

0.5

0.0
0 5 10 15 20 25 30
Time / days
Figure
Figure 6. Cell
6. Cell voltage
voltage of long-term
of long-term one-month
one-month experiments
experiments at aat a fixed
fixed current
current density
density andand temperature.
temperature.
◦
75 C,75 1°C, 1 atm.
atm. 300 mA
300 mA −2
cm cm –2
. Full. Full line—cathode:
line—cathode: Ra-Ni,
Ra-Ni, anode:
anode: SS316L.
SS316L. DashDash
dot dot line—cathode:
line—cathode: agedaged
bare-Ni,
bare-Ni, anode:
anode: agedaged bare-Ni.
bare-Ni.

From Figure 6 it can be seen that initially, the Ni–Ni cell had about a 250 mV larger cell voltage
than SS316L–Ra–Ni. This difference grew to 650 mV at the 25th day. The better performances of
SS316L–Ra–Ni were mainly due to a better HER, as can be seen from Figures 4 and 5. The voltage of
SS316L–Ra–Ni oscillated around 0.05 V for 30 d without giving any sign of losses during that period.
Ni–Ni instead, constantly deteriorated with time.
According to literature, pure Ni for water electrolysis deteriorates mainly because of the
Materials 2019, 12, 1336 11 of 17

According to literature, pure Ni for water electrolysis deteriorates mainly because of the adsorption
of metallic or organic impurities that block the effective sites for HER or OER, the decrease of hydrogen
adsorption capacity after it has absorbed a certain amount of hydrogen for HER [81], and the formation
of surface oxide films having poor electronic conductivity for OER [13].
In order to evaluate the cell behavior and to compare it with bibliographic results with more
optimized cell geometries, computational fluid dynamic (CFD) simulations were carried out, as
described in references [8,9]. Input parameters were: the cell geometry, conductivity of the
membrane-electrolyte, and kinetic behavior from Figures 4 and 5. Table 4 compares the experimentally
obtained average value of the cell potential (during one month), the theoretical cell potential, and the
estimated iR, obtained by a primary current distribution (CFD) study, and finally the cell potential that
would be expected with the proposed catalyst (Ra–Ni and SS316L) in a zero gap assembly.

Table 4. Theoretical and experimental cell voltage using Ra–Ni and SS316L electrodes (75 ◦ C, 1 atm.
300 mA cm−2 ).

U cell Exp/V U cell Theo/V Rcell /Ω U cell Zero-Gap/V

1.905 1.935 0.207 1.705

Our results were comparable with others in similar conditions despite the different cell
design [59,82,83] for SS316L–Ra–Ni and for Ni–Ni [84]. Also, these performances compared well with
more advanced catalysts [79,85,86]. If we did not take into account the additional resistance of our cell
design, around 0.207 Ω as estimated by the CFD result, the Raney–Ni as cathode and SS316L as anode
were in agreement with the most efficient catalyst working in zero gap cells [3,79,80,87].

4.3. Anode Corrosion

To understand whether the catalysts showed corrosion behavior during prolonged use, an ICP-OES
(inductively coupled plasma—optical emission spectrometry) analysis was carried out before and after
the long-term electrolysis. Before electrolysis, there were traces of Co and Fe in solution (about 1.2 and
0.24 ppm, respectively). After long-term experiments, the amount of Cr went to 0.4 ppm and that of Fe
to 0.35 ppm. Nickel was in both cases below the detection limit. It can be concluded that at a current
density of 300 mA cm−2 , concentration of 6 M KOH, and temperature of 75 ◦ C there was no corrosion
of the proposed materials at all. Our results were in agreement with corrosion studies for steel and
SS316L under similar conditions [88,89].
However, in preliminary experiments with electrodes that were aged for a shorter amount of time
or used directly, we noticed a slight coloration of the solution when SS316L was used as an anode.
The solution turned to a very faint yellow tint during the experiment and then green at the end. Also,
black powder was found accumulating on the cathode electrode. In the case of the use of SS316L,
this powder was found to be magnetic suggesting magnetite content. However, black powder was
found also when not working with SS316L anodes. We believe that there may be a selective or partial
corrosion of the pristine electrode. However, after a while this corrosion appeared to stop. At the
moment this phenomenon is still subject to research.

5. Conclusions
In this perspective we highlighted some of the pitfalls in the research for alkaline water electrolysis.
The proper correction of the equilibrium potentials for temperature and also for electrolyte concentration
is extremely important. Ohmic drop correction, which is important for high-current experiments,
should be conducted carefully especially in regards to which technique was used to estimate it.
The electrocatalytic activity of Ni to be used as cathode should not be employed as a reference, as
it is in general not good enough; in addition, it can show strong variations with time [81].
Materials 2019, 12, 1336 12 of 17

Whatever evaluation technique is used, polarization measurements made on fresh electrode

samples after a few hours cannot be considered indicative of performance. A preactivation step, or at
least long-term aging in concentrated solutions, is required.
Ni, Co, Cu, NiCu, NiCo, and NiCoCu alloys were synthetized and characterized electrochemically
for HER and OER in 6 M KOH, showing important catalytic properties for commercial applications. It
was demonstrated that alloying Ni with Co or/and Cu resulted in an increased electrocatalytic activity
in the HER when compared to pure Ni, Cu, and Co. This was due to improved intrinsic activity of
the materials. However, these improvements were not comparable with state-of-the-art Raney nickel.
While, for the OER, NiFe(OH)2 and SS316L showed the best performances, with SS316L displaying the
highest stability.
In long-term experiments, Raney-nickel with an SS316L anode outperformed a cell with symmetric
nickel electrodes by more than half a volt, at 300 mA cm−2 and 75 ◦ C, and showed constant voltage
during the one-month experiment. Extrapolating our results to a zero-gap design, our cell had an
estimated voltage of 1.7 V at 300 mA cm−2 .
In our opinion, we are on the way to reaching the goal of accomplishing a cell voltage less than 2
V at current densities of 1 A cm−2 below 100 ◦ C, as mentioned by Pletcher and Li [6].

6. Future Needs and Prospects

From the experience gained during our research in alkaline water electrolysis and a survey of the
literature, we would like to summarize some suggestions:
(a) Show kinetic behavior with regards to overpotentials with proper corrections for the equilibrium
potentials. In the present contribution we give all the tools needed to accomplish this task. In case this
is not possible, remember that the total water splitting difference of potential, contrary to the single
electrode potentials, shows smaller variations with temperature and electrolyte concentration.
(b) Use the appropriate technique in order to estimate the iR correction. We suggest AC impedance
and correct it according to the electrochemical technique employed. However, when possible, minimize
ohmic drop by a good cell design, with a well-positioned Luggin capillary, using concentrated
electrolyte and higher temperatures.
(c) Compare results with the best-known catalyst. Bare Ni is not a good catalyst for hydrogen
evolution, and it can show erratic behavior. Compare instead with a well-aged or pre-activated Raney
nickel electrode.
(d) Make experiments in conditions closer to industrial situations (high electrolyte concentration
and above room temperature), and test stability of the materials for at least one week.
Looking at the polarization curves, we think that the community should focus on catalysts for
OER, as the overpotentials required for the same current density is at least double than that for HER.
Also, to improve the efficiency of alkaline water electrolysis further, research and development efforts
focusing on the development of optimized cell designs and effective electrolyte additives, use of
physical/chemical electrode modifications for OER, and appropriate management of the gas bubble
phenomena are still required.

Author Contributions: Conceptualization, A.N.C. and A.B.; Methodology, A.N.C.; Software and validation,
A.N.C. and A.B.; Investigation, A.N.C.; Writing—original draft preparation, A.N.C. and A.B.; Writing—review
and editing, A.N.C., H.H.G., and A.B.; Supervision, H.H.G.; Project administration, H.H.G.
Funding: This research was funded by Commission for Technology and Innovation (CTI) and EXEN Sàrl of
Switzerland, project number 17748.1 PFEN-IW.
Acknowledgments: This work was supported by the Agencia Nacional de Promoción Científica y Tecnológica
(ANPCyT), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), and Universidad Nacional
del Litoral (UNL) of Argentina. The authors thank Dr. Heron Vrubel for helpful discussions and suggestions.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.
Materials 2019, 12, 1336 13 of 17

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