1/29/2018 Electrolyzer modules with a) unipolar and b) bipolar cell configurations

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One of the charge transfer steps (Eqs. 33 and 34) is the rate con- trolling step. A slow electron transfer step
determines the reaction at low temperatures. On the other hand, a slow recombination step (Eq. 35) controls the
reaction at high temperatures on Ni electrode. 72,73 Fe and Ni alloys have been found to be able to reduce the
oxygen overpotential to some extent. 74 The reaction rate decreases with increasing activation energy, E a ;
therefore, reducing E a is crucial for more ef cient water electrolysis. In general, E a increases with j, but it can be

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lowered using appropriate electrocatalysts. 42 The overpotential for oxygen evolution is more dif cult to reduce
than that for hydrogen evolution, because of its complex mechanism and irreversibility. It is generally believed that
few noble metal compounds are thermodynamically stable at a low pH and high potential. Nevertheless, acid
solutions or PEMs have been considered as electrolytes in water electrolyzers because acidic media show high ionic
conductivity and are free from carbonate formation, as compared with alkaline electrolytes. 75 Noble metals as
electrocatalysts for OER in acidic media were initially examined by polarization techniques. Ruthenium (Ru) and
iridium (Ir) showed high activity toward OER, but metallic elements were passivated immediately when they reached
higher anodic potentials. 76–81 Then again, metal oxides were of interest because the oxide layer anodically grown
on the metal surface is less stable than that formed by other procedures. A thick lm of ruthenium oxide (RuO 2 )
fabricated on the substrate as a dimensionally stable anode (DSA) in water electrolyzers exhibited high
electrocatalytic activity, depending on adsorption of chemical species, concentration of intermediates, and
morphology. 82–84 However, it was pointed out that the formation of ruthenium tetroxide (RuO 4 ) by further
oxidation of rutile RuO 2 during anodic processes increases kinetic losses at the anode signi cantly. In contrast,
iridium oxide (IrO 2 ) lms were very stable even at potentials close to 2 V, despite showing higher overpotential for
OER than RuO 2 lms. IrO 2 shows higher stability and preferentially evolves molecular oxygen rather than being
oxidized further. 85 To obtain synergistic effects from different metal oxides, a variety of mixed metal oxides were
developed. Ruthenium–iridium oxide showed improved electronic properties and suppressed the formation of RuO 4
; alloying the above two metals with tantalum (Ta) enhanced OER kinetics and the addition of tin (Sn) resulted in a
metastable mixed oxide. 86,87 Recently, Ru-rich Pt electrocatalysts and titanium (Ti)- or titanium carbide (TiC)-
supported electrocatalysts for OER have been suggested. 88,89 Bifunctional electrocatalysts, which can work for
both oxygen evolution and oxygen reduction, have also been proposed for water electrolysis. A typical bifunctional
electrocatalyst is composed of a noble metal oxide such as IrO 2 . For unsupported bifunctional electrocatalysts,
Pt–MO x (M = Ru, Ir, Na), bimetallic (e.g., Pt–Ir), and trimetallic (e.g., Pt 4.5 Ru 4 Ir 0.5 ) materials have been
developed. 90–93 On the other hand, to enhance the electrochemical surface area and electronic properties of the
anode, several supported bifunctional electrocatalysts have been proposed, with IrO 2 -supported Pt
electrocatalysts, for example, demonstrating high electrocatalytic activity toward OER. 94 Signi cant advances in
the development of novel OER electrocatalysts have been made, but considerable challenges still remain,
particularly concerning catalysts’ cost and durability. The water electrolyzer potential accounts for both anode and
cathode reactions. The overpotentials from hydrogen and oxygen evolutions are the main sources of reaction
resistances. The other obvious resistance at high current densities is the Ohmic loss in the electrolyte, which
includes resistances from the bubbles, diaphragm, and ionic transfer. Identifying these resistances is vital to
enhance the ef ciency of water electrolysis. Electrical resistances lead to energy waste in the form of heat
generation, according to Ohm’s law. The electrical resistances in a water electrolysis system have three main
components: (i) resistances in the system circuits; (ii) mass transfer phenomena, including ion transfer within the
electrolyte; and (iii) gas bubbles covering the electrode surfaces and the diaphragm. Resistances in the circuit are
determined by the type and dimen- sion of the material, its preparation method, and the conductivity of each
individual component of the circuit, including wires, connectors, and electrodes. These resistances can be reduced
by decreasing the length of the wire, increasing its cross-sectional area, and adopting more conductive wire
materials. Ionic transfer within the electrolyte depends on the electrolyte concentration, distance between
electrodes, and membrane. Ionic resistance can be minimized by changing the electrolyte concentration or adding
appropriate additives to increase its conductivity. Presence of bubbles in the electrolyte and on the electrode
surface also causes additional resistances to the ionic transfer and electrochemical reactions. The effective
resistance of the membrane, used to separate the produced hydrogen and oxygen gases, is generally 3–5 times
higher than the resistance of an equivalent thickness of electrolyte solution. 59 Energy losses in the electrical circuit
are always relatively small, but those due to ionic transfer become more signi cant at higher current densities.
Formation of gas bubbles on the electrode surface contribute signi cantly to the total energy loss. Convective mass
transfer also controls ionic transfer, heat dissi- pation and distribution, and the action of bubbles in the electrolyte.
The viscosity and ow of the electrolyte play important roles in mass transfer, temperature distribution, and size,
detachment, and rising velocity of bubbles, in turn in uencing the current and potential distribution in the
electrolysis cell. The concentration of the electrolyte increases as the electrolysis progresses, leading to an increase
in the solution viscosity. Water is usually added continuously to the system to maintain a constant electrolyte
concentration and thus a constant viscosity. Better mass transfer leads to higher reaction rates, but not necessarily
to increased hydrogen production. A higher reaction rate generates larger amounts of gas bubbles, which can hinder
the contact between the electrode and the electrolyte. Mechanical recirculation of the electrolyte solution
accelerates the detachment of gas bubbles and brings them to the gas collectors. Electrolyte recirculation is also
important to prevent concentration gradients in the cell and dis- tribute heat evenly within the electrolyte. At the
startup, electrolyte recirculation can be used to heat up the electrolyte to the operating temperature, usually 80‐90
°C. 57,95 Considering that the bubble phenomenon is the major source of electrical resistances in the cell,
minimizing its effect is critical to improve the electrolyzers’ ef ciency. During electrolysis, hydrogen and oxygen gas
bubbles are formed on the surfaces of the cathode and anode, respectively, and are detached from the surface only
when they grow big enough. The bubbles’ coverage reduces the contact between the electrolyte and the electrode,
thereby blocking electron transfer and increasing the Ohmic loss of the whole system. Detachment of the bubbles
also depends on the electrode wettability, i.e., on the electrolyte replacement at the electrode/electrolyte interface.
96,97 Appropriate coatings can be applied on the electrode surface to make it more hydrophilic, thereby reducing
the surface coverage by gas bubbles. Another approach is based on the addition of surfactants to the electrolyte
solution to reduce its surface tension and facilitate detachment of bubbles from the electrodes. In summary, the
bubble effect is a problem that has always to be dealt with, by modifying the electrode surface, reducing the
electrolyte surface tension, or using mechanical uid circulation to force the gas bubbles to leave the cell. Much

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work has been devoted to the bubble behavior in electrolysis systems, 96,98–101 but further studies are still
required to minimize its negative effects. To compare different water electrolysis systems, it is necessary to discuss
a number of practical parameters relevant to the performance of water electrolyzers, including electrolysis cell
con guration, operating conditions, and a few external requirements. Regarding the cell con guration, electrolyzers
may be constructed in either unipolar or bipolar design (Figure 8). A unipolar (or “tank- -type”) electrolyzer (Figure
8a) consists of alternate positive and negative electrodes held apart by porous separators, i.e., membranes. Positive
electrodes are all coupled together in parallel, as are the negative electrodes, and the whole assembly is immersed
in a single electrolyte bath (“tank”) to form a unit cell. A plant-scale electrolyzer is then built up by connecting these
units electrically in series. The total voltage applied to the whole electrolysis cell is the same as that applied to the
individual unit cells. On the other hand, in a bipolar electrolyzer a metal sheet (or “bipole”) connects electrically
adjacent cells in series. As seen in Figure 8b, the electrocatalyst for the negative electrode is coated on one face of
the bipole and that for the positive electrode of the adjacent cell is coated on the reverse face. In this case, the total
cell voltage is the sum of the individual unit cell voltages. Therefore, a series-connected stack of such cells forms a
module that operates at a higher voltage and lower current than the tank-type (unipolar) design. To meet the
requirements of a large electrolysis plant, these modules are connected in parallel so as to increase the current.
These two different cell con gurations present different electrode reactions. For the unipolar con guration, the
same electrochemical reaction (either the HER or the OER) occurs on both sides of each electrode. On the other
hand, in the bipolar con guration, two different reactions (HER and OER) take place simultaneously on the opposite
sides of each electrode not directly connected to the power source. This means that one side of each electrode acts
as a cathode and the other as an anode (although both sides are at the same potential), with the exception of the
two end electrodes that are connected to the DC power source. The resulting cell voltage for these two basic
con gurations is quite different. For typical industrial processes, the unipolar con guration presents a cell voltage of
about 2.2 V and the bipolar con guration has a value of 2.2 × (n − 1) V (where n is the number of electrodes). 1
Owing to the simplicity of the unipolar con guration, this type of electrolyzer is easy to fabricate and requires low
maintenance, but presents high electrical currents at low voltages, causing large Ohmic losses. On the other hand,
the bipolar con guration has lower Ohmic losses in the electrical circuit connectors; however, it demands much
higher precision in its design and manufacturing to prevent electrolyte and gas leakage between cells. 1 The gap
between electrodes must also be considered during cell design. 102 It corresponds to the distance that the ions
have to travel within the electrolyte. 103 A smaller gap has the advantage of less resistance to ionic transportation.
However, if the gap is too small, it can induce electric sparks, posing an explosion hazard. An optimum electrode
gap must be identi ed for each particular cell. The electrolyte ow forces convective mass transfer in the cell. At
high current densities, electrochemical reactions are limited by the electrolyte mass transfer. Stirring and/or
inducing turbulence reduces the concentration gradients in the electrolyte and enhances mass transfer. An
electrolyzer’s operating cell voltage is directly related to its energy consumption and electrical ef ciency. The cell is
considered inef cient if a higher voltage is required to produce an equivalent hydrogen mass, while keeping the
current constant. The operating current density also de nes the electrolyzer’s energy ef ciency. Conventional water
electrolyzers generally run at current densities ranging from 1000 to 3000 A m −2 . The current density determines
the rate of hydrogen production, with higher current densities leading to higher rates of the electrochemical
reactions. However, fast bubble formation resulting from an increased rate of gas production also increases the
overpotential due to the bubbles’ resistance. Therefore, current density should be kept within a certain range, with
compro- mises between the gas production rates and the energy ef ciency. The operating temperature is another
important parameter. Conventional alkaline water electrolyzers are designed to run at temperatures of around 80‐90
oC. Increasing the operating temperature has the advantage of decreasing the equilibrium cell voltage. However,
high temperatures increase water loss due to evaporation and require highly resistant materials to maintain the
equipment’s structural integrity. 57 Also, heat management and the material required for making the diaphragm
bring more engineering issues at higher operating temperatures. The pressure at which the electrolyzer operates
should depend on the end use of the produced hydrogen. Cells operating at an elevated pressure of 3.5 MPa reduce
bubble sizes, thereby minimizing the Ohmic losses. However, the ef ciency of pressurized cells is not signi cantly
superior to that of ambient pressure cells. 43 Moreover, these cells work with higher proportions of dissolved gas,
requiring a more endurable diaphragm. The type and concentration of the electrolyte de nes the ionic conductivity
of the solution and, consequently, the ionic transfer in the cell. KOH (25‐30 wt.%) is adopted widely in commercial
electrolyzers. 104 It is essential for the electrode materials to be stable in highly corrosive alkaline environments, to
minimize the electrolyzer’s operation and maintenance costs. Noble metals have good resistance to corrosion by
alkalis and high electrocatalytic activity, but are too expensive for widespread applications in water electrolysis. 38
Transition metals such as iron and copper have good electrocatalytic activity but are less resistant to alkali attack.
Ni is considered to be one of the best electrode materials for alkaline water electrolysis, with both good resistance
to alkali attack and high electrocatalytic activity, while not being too expensive. The function of the membrane is to
separate the produced hydrogen and oxygen gases while still allowing ionic transfer. Globally, the bene ts of
separating the gases compensate for the Ohmic resistance caused by the presence of a diaphragm. Current
research on separators for alkaline water electrolyzers is directed toward the development of new materials with low
electrical resistance and high corrosion stability. 105 Water quality is a central factor to ensure long-life operation of
an electrolyzer. Impurities can accumulate in the cell, and deposit on the electrode surface and in the membrane,
thus hindering mass and charge transfer. 106 The highly alkaline environment in the electrolysis cell requires the
concentrations of magnesium and calcium ions to be suf ciently low to avoid precipitation of their hydroxides.
Deposition of these compounds is ruled by the solubility product constant (K sp ), which is the limiting value for
precipitation to occur. 31 When the concentration of these impurities reaches this value, deposition takes place. In
addition, when the current density exceeds the so-called limiting current of hydroxyl ions, 107 chloride ions present
in solution are oxidized to chlorine at the anode surface, which is extremely corrosive to most metallic components

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of the electrolyzer. Electrolyzers of different scales are designed to meet the different needs for hydrogen.
Commercially, an electrolyzer can vary from several kW to several hundred MW in terms of power consumption.
43,108 Electrolyzer technologies can be compared in terms of their energy ef ciency or hydrogen production
ef ciency. For low-temperature alkaline water electrolysis, a net ef ciency, η net , of around 50% is considered to be
good. 109 On the other hand, η H2yield is useful when considering hydrogen production per unit volume at a unit
time; a value of about 2.3 m 3 m −3 h −1 kWh −1 is typical for a unipolar water electrolyzer. 43 In terms of safety, the
whole system, including the membrane, should be designed carefully keeping in mind the ammability of hydrogen
and oxygen mixtures. Also, due to the corrosive nature of the alkaline electrolyte, leakage may occur at the
connections and seals of the electrolyzer. The bipolar cell con guration, having a more complex design, poses a
higher risk of electrolyte leakage than the unipolar con guration. Materials used for cell construction determine the
durability of the electrolyzer. These materials should be resistant to highly alkaline electrolytes. Since corrosion is
normally more severe at the joints and connections, joint sealant materials must be stable under the operating
conditions. 110 As shown in previous sections, water splitting is one of the most signi cant reactions in
electrochemistry, being involved in numerous applications, namely those concerning electrochemical energy storage
and conversion. 52,111,112 Considering that electrode reactions are the major causes of energy losses, the exact
mechanism of the electrochemical processes has been pursued consistently for years, 113–116 to allow designing
of highly ef cient electrolytic cells, necessarily with better electrocatalysts. 117 However, the conventional theories
in electrochemistry, 52 such as the Gouy‐Chapman theory, the Nernst equation, and the Butler‐Volmer model, do not
fully allow the atomic-level understanding of the HER/OER at the electrolytic cell. In particular, the detailed
mechanism of electrocatalysis has been extremely dif cult to analyze, mainly because of the complex nature of the
geometric and electronic structures of electrodes and solution. 65,118 Therefore, it has been realized that rigorous
quantum mechanical (QM) treatment is essential to obtain reliable energetics for electrochemical reactions. QM
treatment of the electrochemical interface, based on both computational facilities and theoretical models, 119–121
enables a better understanding of the electrolytic processes, where the electrochemical potentials, water
environment, and electrodes are all taken into account explicitly. Accordingly, many studies are progressively
revealing the atomic-level details of the electrode reactions at water electrolysis cells. 122–125 Early electrolysis
cells were about 60‐75% ef cient. However, the current small-scale, best-practice gure is close to 80‐85%, with
larger units being a little less ef cient (ca. 70‐75%). However, it should be noted that when electricity generated from
thermal power stations is used, the overall ef ciency is only about 25‐30% for the conversion of fossil fuel to
hydrogen. This is not a very attractive return on the invested energy. Nevertheless, R&D efforts add continuous
innova- tions to the existing concepts of water electrolysis. Most of the recent research is focused on reducing
system resistances and, consequently, energy losses. 28,126 In this way, one would approach the nal goal of
“manufacturing” hydrogen as a clean and economic energy carrier. Truly clean hydrogen can be obtained only
through the use of renewable energy forms. This can be accomplished by photochemical water splitting or through
intermediate production of electricity, using wind resources or PV cells, followed by water electrolysis. Use of
arti cial photosynthetic systems poses one of the major challenges in the eld of chemistry. 127 The simplest and
practical approach to produce solar fuels using arti cial photosynthetic systems is to mimic the natural
photosynthetic process. Light harvesting leads to charge separation, followed by charge transport to deliver the
oxidizing and reducing equivalents to catalytic sites where evolution of hydrogen and oxygen occurs. Figure 9
presents the basic features of an arti cial photosynthetic system: 128 (i) an antenna for light harvesting, (ii) a
reaction center for charge separation, (iii) catalysts as interfaces between the charge-separated state and the
substrate, and (iv) a membrane to provide physical separation of the products. Complexity of the natural
photosynthetic systems is largely related to their living nature. It is known that single photosynthetic functions, such
as photoinduced energy and electron transfer, can be copied by simple arti cial systems. However, nature tells us
that ef cient conversion of light into chemical energy requires the invol- vement of supramolecular structures with
precise organization in the dimensions of space (relative location of the components), energy (excited-state
energies and redox potentials), and time (rates of competing reactions). This organization is a result of natural
evolution and is dictated by complex intermolecular interactions. Its transposition to arti cial systems can be
imposed by molecular engineering using covalent or noncovalent bonding. 129 Although progresses have been
accomplished in each individual component of arti cial photosynthesis used for the cleavage of water into
hydrogen and oxygen, integration of those components in a working system has not yet been achieved.
Nevertheless, photochemical conversion of solar power into electrical power is now possible using PV cells and
photoelectrochemical (PEC) cells. 130-133 PV cells capture photons by exciting electrons across the band gap of a
semiconductor. This process generates electron–hole pairs that are separated subsequently, typically by p–n
junctions introduced by doping. 134 In the n-type regions of the device, conduction-band electrons can ow easily to
and from cell contacts, whereas valence holes cannot; the p-type regions have the opposite properties. Such an
asymmetry causes a ow of photogenerated electrons and holes in opposite directions, generating a potential
difference at the external electrodes. First-generation PV cells, which account for 85% of the current market, 135 are
based on expensive polycrystalline silicon wafers. Less expensive PV modules have ef ciencies of 15–20% and a
lifetime of the order of 30 years. 134 However, for solar electricity to be cost competitive with fossil-based electricity
at utility scale, manufacturing costs must be reduced substantially. This goal has been reached partially with
second-generation cells, which are based on thin lms of less expensive materials such as amorphous or
nanocrystalline Si, CdTe, or CuInSe 2 . However, further research is needed to improve the ef ciency of these cells in
order to make them economically competitive. A practical method for applying PV electrolysis was rst reported by
Fujishima and Honda in 1972. 136 A titanium dioxide (TiO 2 ) electrode captures the energy of ultraviolet (UV) light
and converts it into electricity, which is to be used in the direct decomposition of water into hydrogen and oxygen.
With the increasing interest in renewable energies, PV electrolysis has become a major contributor to hydrogen
production. A PV electrolysis system includes a PV cell and an electrolysis circuit. The photoelectrodes absorb

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energy from UV light and release electricity required for water splitting. Much research is currently devoted to
developing photoelectrochemically active semiconductor materials. The low ef ciency of the PV electrolysis (~2‐
6%) prevents its use for large-scale hydrogen production. 137 Low solar energy density, variations in energy content
of solar radiation, low operating current density, and expensive and unstable electrode materials make large-scale
application of PV electrolysis infeasible at this stage. 138 PEC cells, also known as dye-sensitized solar cells or
Grätzel cells, 139 are based on the sensitization of wide band gap semiconductors by dyes capable of using solar
energy (i.e., visible light). Although the basic principles of dye sensitization of semiconductors have long been
established, 140 the application of such techniques to light–energy conversion became appealing only after new
nanocrystalline semiconductor electrodes of very high surface area had been developed. 141,142 The working
principle of a dye-sensitized solar cell is shown in Figure 10. 139 The system comprises a photosensitizer S linked in
some way (usually, by –COOH, –PO 3 H 2 , or –B(OH) 2 functional groups) to the semiconductor surface, a solution
containing a redox mediator A, and a metallic counter electrode. The sensitizer is rst excited by light absorption.
The excited sensitizer then injects, in the femto- to pico-second timescale, an electron into the conduction band of
the semiconductor. The oxidized sensitizer is reduced by a relay molecule, which then diffuses to discharge at a
conductive glass counterelectrode. As a result, a photopotential is generated between the two electrodes under
open- -circuit conditions, and a corresponding photocurrent can be obtained on closing the external circuit by an
appropriate load. Therefore, the main difference of PEC cells from photosynthetic systems is that the redox
potential energy of the charge-separated state is not stored in products of subsequent reactions, rather it is used
directly to produce a photocurrent. 143,144 High-temperature electrolysis (HTE), also known as steam electrolysis,
is performed using a solid oxide electrolysis cell (SOEC), as shown in Figure 11. It adopts a solid oxide, as the
electrolyte, in a process that is essentially the reverse operation of a solid oxide FC. An SOEC operates at elevated
temperatures, typically between 500 and 850 oC, where water splitting is favored thermodynamically. 145 Steam
passes through the cathode side of the solid electrolyte where the water gas molecules are reduced to hydrogen,
releasing oxide ions in the process (Eq. 37). These oxide ions migrate through the electrolyte to the anode side
where they combine to form oxygen molecules, releasing electrons 145,146 (Eq. 38). Cathode H 2 O + 2 e − H 2 + O
2− (37) Anode O 2− 1⁄2 O + 2 e − (38) Hydrogen production via the SOEC generally involves consumption of less
electrical energy than conventional low-temperature water electrolyzers, owing to the improved thermodynamic and
kinetic operating conditions at high temperatures. 147 For instance, for an average current density of 7000 A m −2
and an inlet steam temperature of 750 oC, the electrical energy consumption of the stack will be around 3 kWh per
normal m 3 of hydrogen, which is signi cantly less than the energy consumption of a typical low-temperature
alkaline water electrolyzer (4.5 kWh). 148 However, it should be emphasized that this comparison does not take into
account the circulation and losses of heating energy. Moreover, HTE must also address stricter temperature control
and safety issues, as well as use of appropriate construction materials. 149–153 Although alkaline water
electrolysis is undergoing continuous improvement, it may currently be seen as a mature technology, with
reasonable ef ciency when compared to other emergent water electrolysis systems. Although PEM electrolyzers
have high ef ciencies, they need to overcome several technical hitches. PV electrolysis faces many engineering
challenges concerning its scale up. An SOEC has to deal with corrosion issues because of its high operating
temperature. It seems that improving the low-temperature alkaline water electrolysis technology, to increase its
ef ciency, is still a more realistic solution for large-scale hydrogen production in the near future. 154 For the
widespread commercial application of alkaline water electrolysis, current research trends are particularly focusing
on the electrodes, electrolytes, ionic transport, and bubble formation. Ni is the most widely used electrode material
for water electrolysis because of its good stability and electrocatalytic activity. However, deactivation of the
electrode material is a major problem in electrolysis, and even Ni is affected by it. Ni electrode deactivation is
caused by the high hydrogen concentration near the electrode, which leads to the formation of a Ni hydride phase at
the surface. Iron coatings are known to inhibit the formation of the Ni hydride phase and hence prevent electrode
deactivation. 39 Dissolved vanadium species have the ability to activate Ni cathodes during hydrogen evolution in
alkaline media. 155 Electrode materials affect the activation energy of the electrochemical reaction. Electrocatalysts
are used to facilitate the charge transfer and/or to enhance the rate of the chemical reactions. They reduce the
activation energy of the process by decreasing the associated overpotential. The effect of the electrocatalyst
depends on the electronic structure of the electrode. Ni, Pd, and Pt with d 8 s 2 , d 10 s 0 , and d 9 s 1 electronic
con gurations, respectively, exhibit minimum η values for the HER. In contrast, Zn, Cd, and Hg with d 10 s 2
electronic con guration show the maximum values. The spillover theory in electrocatalysis, by Bockris et al., 1
explains the interactions between substances. The Brewer–Engel valence bond theory has also been used
intensively to study hydrogen electrodes. Jaksic has reported 156–158 that by alloying metals of the left half of the
transition series in the periodic table with empty or less lled d-orbitals with metals of the right half of the series
with more lled d-bands, maximum bond strength and stability of the intermetallic alloy phases could be achieved.
This leads to a well-pronounced synergism in electrocatalysis. It is implied that some of the electrons of the metal
with more lled d-bands are shared with the metal with less lled or empty d-orbitals. 156,157 The observed
synergistic effect normally exceeds the performance of the individual parent metals and approaches reversible
behavior within a wide range of current densities. Therefore, alloys formed by metals with different electronic
distributions are adopted to improve the electrocatalytic activity of electrodes. 159–168 Santos et al. studied
hydrogen discharge using pla- tinum–rare earth (Pt–RE) alloys (RE = Ho, Sm, Ce, Dy) and found out that Pt–RE
alloys of equiatomic compositions exhibit superior performances than single Pt electrodes. 167,168 Cathodes
containing Pt– Mo alloys also presented much higher activities than those containing individual parent metals. 169
A composite cathode of Ni, Fe, and Zn, prepared by electrodeposition, showed good stability for up to 200 h at a
current density of 1350 A cm −2 . This composite also presented good activity in 28% KOH, at 80 oC; its
overpotential was ~100 mV, which is signi cantly lower than that of mild steel (~400 mV). 170 Noble metal oxides
are commonly used as electrocatalysts. Ruthenium dioxide (RuO 2 ), iridium dioxide (IrO 2 ), and mixed oxides

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containing these two noble metals have been proved to have high electrocatalytic activity for the OER. 171–177 Ir x
Ru y Ta z O 2 as an anode electrocatalyst achieved an overall cell voltage of 1.57 V at 1 A cm −2 at 80 °C, with an
energy consumption of 3.75 kWh N m −3 H 2 and ef ciency of 94%, for a total noble metal loading of less than 2.04
mg cm −2 . 47 However, there are some non-noble, less expensive metals that also present electrocatalytic activity
and are being introduced for use in oxygen 178–185 and hydrogen 165,166,186–191 evolution reactions.
Additionally, during designing an electrode, it is normally doped or coated with more stable and active layers. The
doping material may be chosen from a wide range of metals. 192 For example, Li doping increases the electrical
conductivity of the electrode material and also its roughness factor (when adding up to 3% Li), favoring the OER. 193
A single-cell electrolyzer using a Li-doped Co 3 O 4 anode electrocatalyst exhibited a current density of 300 mA cm
–2 at a voltage of 2.05 V at 45 oC. The Li 0.21 Co 2.79 O 4 anode showed good stability in continuous operation for
10 h at 300 mA cm −2 and 30 °C. 194 Nanostructured electrodes present an enlarged surface area and possess
unique electronic properties. The increased active area of the nanostructured electrode reduces the operating
current density of the electrolyzer. A 25% reduction in overpotential and 20% reduction in energy consumption were
achieved by the use of a Ru nanorod cathode when compared to a regular planar Ru cathode. 55 This improvement
can be ascribed to the increased active area of the nanostructured electrode, which reduced the operating current
density of the electrolyzer. Kamat 132 proposed the use of nanostructures to improve the performance of
photoelectrolysis by enhancing charge transfer, which also have the potential to be applied as electrodes for water
electrolysis. Regarding the electrolyte, and as seen before, most commercial electrolyzers have adopted alkaline
solutions of KOH or NaOH. However, energy consumption during water electrolysis may be reduced signi cantly by
adding small quantities of activating compounds. 195,196 Ionic liquids (ILs) are organic compounds that are liquid
at room temperature; these consist only of cations and anions, and thus possess reasonably high ionic conductivity
and stability. 197 Imidazolium ILs have been used as electrolyte media for hydrogen production through water
electrolysis. Current densities up to 200 A m −2 and ef ciencies higher than 94.5% have been achieved using
imidazolium ILs in conventional electrochemical cells with Pt electrodes at room temperature and atmospheric
pressure. 198 The main problem with ILs is that they normally have high viscosity and low water solubility.
51,199,200 This hinders mass transfer, and leads to low current densities and, consequently, low hydrogen
production rates. ILs with higher conductivities and better water solubility are required to enhance ionic transfer and
improve the water electrolysis process. Research efforts on new electrolyte media for water electrolysis are still
relatively scarce when compared to the huge number of studies devoted to the development of new electrocatalytic
materials. There is an immense potential for improving overall electrolysis ef ciency using electrolyte additives,
which can enhance mass transfer and thus reduce the electrolyte resistance. Addition of electrolyte additives also
affects the af nity between the electrolyte and the electrodes, facilitating bubble management. As discussed before,
formation and transportation of bubbles cause considerable Ohmic losses in the cell. The dissolved gas bubbles
and the gas interfaces between electrodes and electrolyte generate large resistances to water electrolysis. The
bubble phenomena have been studied intensively, 96,201,202 but no mechanisms or models have yet been applied
to alkaline water electrolysis. The contributions of the electrode surface coverage by gas bubbles and the
electrolyte- -phase bubble void fraction to the Ohmic drop have been discussed. 97 Reducing the bubbles’ residence
time on the electrode surface is fundamental to minimize their size and thus reduce their resistance. Hydrophilic
electrodes have higher af nity to water than to gas bubbles. Their application facilitates mass transfer from the
electrolyte to the electrode. Surfactants may be added to the electrolyte to reduce the surface tension. This will
decrease bubbles’ size and accelerate their detachment from the electrode surface. The added surfactants must be
inert to the electrochemical reactions 203 and stable during the whole process. The electrode surface may also be
modi ed mechanically by introducing slits and holes on it to promote the escape of the gas bubbles. To avoid gas
trapping in the holes, the typical diameter for electrode perforation in alkaline water electrolysis is 0.1 and 0.7 mm
for hydrogen and oxygen, respectively. 38 Forced mechanical circulation of the electrolyte solution can also help
sweeping the bubbles off the electrode’s surface. The electrolyte circulation speed should be high enough to
promote mass transfer and eliminate concentration gradients. In summary, the overall performance of novel
electrolyzers is impressive, particularly regarding their high operating current densities and relatively low cell
voltages, and further improvements are expected to occur. Alkaline water electrolysis, powered by renewable energy
sources (e.g., sun, wind, and waves), can be integrated into a distributed energy system to produce hydrogen for end
use or as an energy storage medium. Compared to the current major methods used for hydrogen production,
alkaline water electrolysis is generally seen as a simpler technology; however, it still needs much work to improve its
present ef ciency. Further research is required to overcome durability and safety issues that still block the
widespread use of alkaline water electrolysis. The fundamentals of water electrolysis have been examined and
performances of various water electrolysis designs have been compared. Thermodynamic and kinetic approaches
to the alkaline water electrolysis technology have been envisaged. The resistances that hinder the electrolysis
ef ciency have been identi ed, which include resistances generated by gas bubbles, activation energies of
electrochemical reactions, mass transfer, and electrical resistances in the circuit. The effect of the bubbles’
resistance can be minimized by modifying the electrode and/or using electrolyte additives. The reaction
overpotential may be adjusted by the choice of a suitable electrode material. Mass transfer resistances can be
reduced substantially through electrolyte circulation. A clear awareness of the involved resistances is vital to
improve the electrolyzer’s ef ciency, especially when working at high current densities. Some practical
considerations on the electrolyzers’ development indicate that alkaline water electrolysis is a viable method for
hydrogen production. The historical background of water electrolysis technology has been presented to shed light
on what should be the future trends to follow. To improve the ef ciency of alkaline water electrolysis further, R&D
efforts focusing on the development of new electrocatalysts and effective electrolyte additives, use of physical/
chemical electrode modi cations, and appropriate management of the gas bubble phenomena are urgently required.
FCT, the Portuguese Foundation for Science and Technology, is gratefully acknowledged for funding the project

https://www.researchgate.net/figure/Figure-8-Electrolyzer-modules-with-a-unipolar-and-b-bipolar-cell-configurations_262617097_fig8 6/8
1/29/2018 Electrolyzer modules with a) unipolar and b) bipolar cell configurations
Functional Materials for Electrolytic Hydrogen Production (PTDC/SEN- ENR/121265/2010). D. M. F. Santos would
also like to thank FCT for postdoctoral research grant SFRH/BPD/63226/2009.

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Hydrogen production by alkaline water electrolysis

Article Dec 2012 · Química Nova
D. M. F. Santos · César Sequeira · José Luís Figueiredo

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Citations

... This last con guration has been considered as the most successful one, containing all the elements and
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https://www.researchgate.net/figure/Figure-8-Electrolyzer-modules-with-a-unipolar-and-b-bipolar-cell-configurations_262617097_fig8 7/8
1/29/2018 Electrolyzer modules with a) unipolar and b) bipolar cell configurations
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... Electrolysis is a process that occurs when direct current passes through an electrolytic system composed of an
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