Sci. Bull.
com
DOI 10.1007/s11434-016-1023-0
Review
Research progresses of cathodic hydrogen evolution in advanced
lead–acid batteries
Feng Wang • Chen Hu • Min Zhou •
Kangli Wang • Jiali Lian • Jie Yan •
Shijie Cheng • Kai Jiang
Received: 4 November 2015 / Revised: 5 January 2016 / Accepted: 22 January 2016
Ó Science China Press and Springer-Verlag Berlin Heidelberg 2016
Abstract Integrating high content carbon into the nega-
tive electrodes of advanced lead–acid batteries effectively
eliminates the sulfation and improves the cycle life, but
brings the problem of hydrogen evolution, which increases
inner pressure and accelerates the water loss. In this
review, the mechanism of hydrogen evolution reaction in
advanced lead–acid batteries, including lead–carbon bat-
tery and ultrabattery, is briefly reviewed. The strategies on
suppression hydrogen evolution via structure modifications
of carbon materials and adding hydrogen evolution inhi-
bitors are summarized as well. The review points out
effective ways to inhibit hydrogen evolution and prolong
the cycling life of advanced lead–acid battery, especially in
high-rate partial-state-of-charge applications.
Keywords Lead–carbon battery  Ultrabattery 
Hydrogen evolution reaction  Hydrogen inhibition
Electronic supplementary material The online version of this
article (doi:10.1007/s11434-016-1023-0) contains supplementary
material, which is available to authorized users.
F. Wang  M. Zhou  K. Wang (&)  J. Lian  J. Yan 
S. Cheng  K. Jiang (&)
State Key Laboratory of Advanced Electromagnetic Engineering
and Technology, School of Materials Science and Engineering,
Huazhong University of Science and Technology,
Wuhan 430074, China
e-mail: klwang@hust.edu.cn
K. Jiang
e-mail: kjiang@hust.edu.cn
C. Hu
China Electric Power Research Institute, Beijing 100192, China
www.scibull.
www.springer.com/scp
Materials Science
1 Introduction
Lead–acid battery has been commercially used as an
electric power supply or storage system for more than
100 years and is still the most widely used rechargeable
electrochemical device [1–4]. Most of the traditional valve-
regulated lead–acid (VRLA) batteries are automotive
starting, lighting and ignition (SLI) batteries, which are
usually operated in shallow charge/discharge cycles.
Recently, lead–acid battery has attracted considerable
attentions for hybrid electric vehicles (HEVs) and energy
storage applications because of low initial cost, simplicity
of design, reliability and relative safety, and high recycling
efficiency [5–8]. However, the cycle life of VRLA batteries
under such applications has been found to be much shorter
than the design life [9, 10]. The major failure mode has
been identified to be the negative progressive sulfation at
high discharge rate or under high-rate partial-state-of-
charge (HRPSoC) cycling [11]. It can be attributed to the
following aspects. First, the formation of a thin-layer lead
sulfate under HRPSoC hinders further discharge, which
will grow progressively and thus lead to irreversible hard
sulfation in the negative plates. Second, high rate charge
increases the mass transport overpotential of the primary
reactions, resulting in evolution of hydrogen and oxygen at
negative electrode and positive electrode, respectively [9,
12, 13].
To improve the cycle life of lead–acid batteries, con-
siderable effort has been devoted over many years [14–17].
In 1997, the scientists at Japan Storage Battery Company
found that adding higher than usual levels of carbon to the
battery dramatically reduced the sulfation of the negative
electrode, thereby increasing performance and lifetime [18,
19]. This work has been confirmed by Australia’s Com-
monwealth Scientific and Industrial Research Organization
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 Sci. Bull.

(CSIRO) that raising the concentration of carbon black

from 0.2 wt% to 2.0 wt% in the negative paste produced an
immediate gain in HEV cycle life [10, 20–22].
After high content carbon was discovered to provide
benefits, the focus moved toward the carbon-enhanced
designs. The use of carbon has taken a number of ways,
initially with carbon using as a conductive component of
electrodes and more recently as a capacitive component
[23]. The ‘‘ultrabattery’’ developed by CSIRO and Fur-
ukawa Battery Co. is a hybrid energy storage device, which
combines an asymmetric supercapacitor and a lead–acid
battery in one unit cell, without extra electronic control, as
illustrated in Fig. 1 [22, 24]. The ‘‘ultrabattery’’ exhibits a
significantly improved cycle life over traditional lead–acid
batteries, as well as increased charge power and charge
acceptance. In addition to the above-mentioned device,
high content carbon has also been integrated directly into
traditional lead–acid batteries as an additive in the negative
plates, as shown in Fig. 2 [25]. This lead–carbon battery
has been demonstrated to increase cycle life by an order of Fig. 2 (Color online) Schematic representation of a single cell from
magnitude or more under HRPSoC cycling. the lead–carbon battery [25]
It is widely acknowledged that the addition of carbon
materials can improve the overall electrical conductivity of However, the carbon materials adopted in ultrabattery or
the negative plate, share the charge and discharge currents Pb–C battery have lower overpotentials of hydrogen evo-
with the lead–acid negative plates, restrict the lead sulfate lution especially in acidic electrolyte, which will promote
crystal growth and thus increase the cycle life for lead–acid hydrogen evolution and thus increase the inner pressure
batteries in HRPSoC applications [26, 27]. Figure 3 shows and accelerate water loss of battery [20, 29]. Therefore,
the schematic diagram for the effects of activated carbon inhibition hydrogen evolution is critical to develop high-
(AC) on negative electrode under HPRSoC operation [28]. performance ultrabattery or Pb–C battery [30–32].

Fig. 1 (Color online) Schematic representation of a single cell from the ultrabattery [22, 24]

123
Sci. Bull.
Fig. 3 (Color online) Schematic diagram for the effects of carbon additives on negative electrode sheets under HPRSoC conditions [28]
2 Hydrogen evolution reaction
Hydrogen evolution is a secondary and side reaction in
lead–acid batteries, which influences the volume, compo-
sition and concentration of the electrolyte, and thus the
battery performance. Generally accepted hydrogen evolu-
tion reaction (HER) mechanisms in acid solutions are as
follows:
Electrochemical hydrogen adsorption (Volmer reaction)
H þ M þ e $ MH :
þ
Followed by electrochemical desorption (Heyrovsky
reaction)
MH þ Hþ þ e $ M þ H2 ;
or chemical desorption (Tafel reaction)
2MH $ 2M þ H2 ;
where H* is the hydrogen atom chemically adsorbed on an
active site of the electrode surface (M) [33]. These
pathways are strongly dependent on the electrochemical,
chemical and physical properties of the electrode surface.
The possible rate controlling steps (1, 2 or 3) can be simply
determined by evaluating the Tafel slope from the HER
polarization curve, which has been carefully explained by
Conway and Tilak [34].
The equilibrium potentials of the positive and negative
electrodes in a lead–acid battery and the evolution of
hydrogen and oxygen gas are illustrated in Fig. 4 [35].
When the cell voltage is higher than the water decompo-
sition voltage of 1.23 V, the evolution of hydrogen and
oxygen gas is inevitable. The corresponding volumes
depend on the individual electrode potential or overcharge
voltage. At the beginning, the two curves increase gradu-
ally, indicating that both hydrogen and oxygen generation
reactions occur quite slowly as long as the overvoltage
ð1Þ remains fairly small. When the overvoltage exceeds certain
values, both curves show a steep increase. This means that
both hydrogen and oxygen generation increase substan-
tially, typically during boost charge or equalizing charge.
ð2Þ When the battery is overcharged, hydrogen and oxygen
evolution become the primary reactions that occur, which
accelerate water loss and reduce the cycle life of lead–acid
ð3Þ battery [35]
2Hþ þ 2e ¼ H2 : ð4Þ
It is worth noted that in a lead–acid battery, the oxygen
evolved from the positive plates can diffuse through the
pores of the separators or the headspace of the container to
the negative plates where it is reduced back to water. This
process forms an internal oxygen cycle in the cells. In the
contrast, the hydrogen produced from the negative plates
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Fig. 4 (Color online) Equilibrium potentials of the positive and negative electrodes in a lead–acid battery and the evolution of hydrogen and
oxygen gas [35]
almost cannot be oxidized back to water at the positive
plates because of its poor kinetics. Thus, any hydrogen
evolution during the charging will convert to a permanent
loss of the water from the battery [20, 36].
Compared with lead, carbon material has much lower over-
potential of HER, especially in acidic electrolyte. Therefore,
under the cathodic working conditions of lead–acid battery
(-0.86 to -1.36 V vs. Hg/Hg2SO4, 5 mol/L sulfuric acid),
the carbon electrode can easily cause severe hydrogen evolu
tion at the end of charge, thus resulting in the thermal runaway
or even electrolyte dry out, as shown in Fig. 5 [20].
To address the above-mentioned issue, many efforts
have been made during the past years, structure modifica-
tion of carbon materials or/and the adding of hydrogen
evolution inhibitors have been identified as effective ways
to suppress HER and prolong the cycling life of lead–acid
battery in HRPSoC applications.
3 Structure modifications of carbon materials
The main requirements of carbon additives to negative
plate of lead–acid battery have been summarized by Lam
and co-workers [29]: (1) similar working potential to that
of the lead–acid negative plate; (2) low hydrogen gassing
rate; (3) higher capacity to share the current with the lead–
acid negative plate; (4) long cycle life; (5) sufficient
mechanical strength and ability to produce in the existing
lead–acid factory; and (6) low cost.
The hydrogen gassing rate is mainly influenced by two
properties of an electrode: surface area and surface activity.
In general, the capacitance of carbon increases with surface
area. However, higher surface area may increase hydrogen
reaction exchange current density and promote hydrogen
gassing. To suppress the hydrogen evolution, the effort
123
Sci. Bull.
must be to lower the specific area without sacrificing too
much capacitance. Shi [37] investigated the relationship
between specific capacitance and specific area for activated
microbead carbon and AC fiber and found that the specific
double-layer capacitance of AC did not have a linear
relation with their total surface area. Instead, the specific
capacitance could be described as the addition of two dif-
ferent parts, as shown in Eqs. (5) or (6):
mi ext
C ¼ Cdl Smi þ Cdl Sext ; ð5Þ
or
mi ext
C=Sext ¼ Cdl Smi =Sext þ Cdl ; ð6Þ
ext mi
where Cdl ; Cdl are capacitance per unit area for external
pores and micro pores; Sext, Smi are the surface area con-
tributed by external pores and micropores. Results indicate
that the double-layer capacitance per unit micropore area.
mi ext
Cdl is different from that per unit external surface, Cdl .
The specific double-layer capacitance on the micropore
surface is mainly determined by the property of carbon
basal layer, while the specific double-layer capacitance on
the external surface strongly depends on the surface mor-
phology and possibly also on the functional groups. It
suggests that an increase in specific capacitance may be
realized without increasing the hydrogen evolution rate, by
shifting surface area between micropores and external
pores with total surface area remaining the same.
The surface activity is usually referred to as kinetic
parameters, such as exchange current density of HER (j0),
which is the rate of hydrogen evolution (or oxidation) per
surface area at the potential where the reaction is at equi-
librium (U = 0 V vs. normal hydrogen electrode (NHE) at
standard conditions) [33, 38, 39].
Various carbon nanostructures (carbon nanotubes, gra-
phene, fullerenes and hybrids) with tunable composition
Sci. Bull.
Fig. 5 Operational potentials of a lead–acid negative plate and a carbon-based (e.g., AC) capacitor electrode during discharge and charge [20]
(heteroatom dopants) exhibit widely different exchange
current densities for HER. Prosini et al. [40] studied the
kinetic processes of hydrogen evolution in acid media on
carbon nanotubes (CNTs). The results showed that hydro-
gen can be easily generated with low overvoltage and high
exchange current density. Brennan and Brown [41] com-
pared the activity of HER on the surfaces of vitreous car-
bon and graphite and found that the order of activities was
pyrolytic edge & vitreous carbon [ pyrolytic face. The
difference in activities could not be entirely explained by
relative surface area but was very sensitive to electrode
pretreatment. Wang et al. [42] investigated the effect of AC
surface functional groups on hydrogen evolution reaction
and lead–carbon battery performance. The surfaces of AC
materials were modified with acidic groups (AC-air and
AC-acid) and alkaline groups (AC-alkali and AC-N800).
The results indicated that the alkaline surface groups could
inhibit hydrogen evolution, while AC samples with acidic
functional groups (AC-acid) promoted hydrogen evolution.
However, the acidic groups can also act as the active sites
for lead electrodeposition, which can suppress the hydro-
gen evolution significantly. It suggests that the moderate
acidic functional groups on the AC surface are beneficial
for lead deposition and thus cause effective hydrogen
evolution inhibition.
Heteroatom doping (such as N, B, S and P) has been
attracting increasing attention, as an effective strategy to
tailor the chemical and physical properties of carbon-based
materials, thus influencing the activity of HER [43–47].
Quantum mechanics calculations with hybrid density
functional theory (DFT) indicate that carbon atoms
adjacent to N dopants possess a noticeably high positive
charge density to counterbalance the strong electronic
affinity of the N atom [48]. Hong et al. [49] firstly reported
that the hydrogen evolution rate on AC has been signifi-
cantly suppressed by N doping; therefore, the charge
acceptance and charge retention ability of the ultrabattery
have been markedly improved (Fig. 6).
However, the literature contains conflicting reports
about effects of N doping. Zhang and co-workers [50, 51]
used commercial activated carbon as the base material and
cyanamide as the nitrogen source for doping. The results
indicated that the activity of AC toward the HER has been
enhanced by nitrogen doping, which has been explained by
the increase in the electron density in some of the adjacent
carbon atoms and therefore donates electrons more readily.
The inconsistent results might be attributed to the different
occupation site of nitrogen in carbon lattices. Normally,
when a nitrogen atom is doped into graphene, it has three
common bonding configurations within the carbon lattice,
including quaternary N (or graphitic N), pyridinic N and
pyrrolic N [52–54]. Quaternary is tetrahedral sp3
hybridization, while pyridinic N and pyrrolic N are planar
sp2 hybridization. The spin density and charge distribution
of carbon atoms are greatly affected by the neighbor
nitrogen dopants, which induces the ‘‘activation site’’ on
the graphene surface. The activated site can participate
directly in the catalytic process, such as the HER or ORR,
and thus significantly influence the reaction rate.
Other heteroatoms doping, such as sulfur and phospho-
rus, may have the similar influence on the activity of HER,
but has been rarely investigated. Liu et al. [55] compared
123

Fig. 6 (Color online) Linear sweep voltammetry (LSV) curves (a) and cyclic voltammetry (CV) curves (b) of AC and NAC [49]
pure and phosphorus-doped graphite layer by using a
cluster approach with DFT. The good electro-donor prop-
erties of phosphorus and the strong electron affinity of
phosphorus for positive atoms facilitate the adsorption of
O2 and significantly enhance the rate of the overall oxygen
reduction process, as shown in Fig. 7. It can be predicted
that the electrochemical adsorption process of hydrogen
ions will be inhibited when atoms with negative net charge
decrease because of the insertion of phosphorus atoms.
4 Hydrogen evolution inhibitors
Another effective strategy to suppress hydrogen evolution
or to reduce it to a very low value is to add inhibitors that
may increase the hydrogen overvoltage. Various inorganic
and organic substances have been investigated in the
Fig. 7 (Color online) Net charge for some selected atoms of the H-terminated graphene sheet in its optimized structures. a The ideal (pure)
graphene sheet. b Graphene sheet with one phosphorus atom [55]
123
Sci. Bull.
previous literature [36, 56–60]. Physical mixing or chem-
ical depositing high HER overpotential metal impurities or
metal oxides has been identified to have a substantial
inhibition effect by occupying the reactive sites.
Pierson et al. [61] investigated that the effects of various
impurities added to the electrolyte on gassing and identified
that the most deleterious elements toward gassing were
tellurium, antimony, arsenic, nickel, cobalt and magne-
sium. Tin, zinc, cadmium, calcium, lithium and mercury
had no detectable effect at the maximum concentrations.
Silver, bismuth, copper, cerium, chromium and molybde-
num were acceptable at levels of 500 ppm or less in the
electrolyte. Lam et al. [62] systematically evaluated the
influence of many different impurities on the hydrogen and
oxygen evolution currents in lead–acid batteries on float
charge. Table S1 (online) shows the effect of the increase
or decrease in the oxygen or hydrogen gassing current in
Sci. Bull.
mA/Ah of battery capacity per ppm of the impurity element
[63]. It has been found that only bismuth and zinc can
suppress gassing, while cadmium, germanium and silver
almost have no effect [62, 63]. Zhao et al. [64, 65]
demonstrated that adding Bi2O3, Ga2O3 or In2O3 into
electrochemical active carbon could effectively increase the
overpotential of hydrogen evolution, decrease the evolution
rate of hydrogen and thus prolong the cycle life of batteries
under HRPSoC conditions, as shown in Fig. S1 (online).
Some organic substances have also been found to
exhibit an inhibition effect on hydrogen evolution,
including derivatives of benzaldehyde, benzoic acid and
benzene [66]. The major problem lies with selecting a
suitable inhibitor that is thermally, chemically and elec-
trochemically stable under battery working conditions. And
the inhibition mechanism of various inhibitors is still
unclear and needs further investigation.
5 Conclusions and perspectives
For developing advanced lead–acid batteries, the addition
of high content of carbon into the negative electrode of
lead–acid battery overcomes the problem of sulfation, but
results in hydrogen evolution, which accelerates the elec-
trolyte loss and negatively influences the battery perfor-
mance. To solve this problem, two main strategies have
been proposed: (1) modifying the carbon structures. The
HER is strongly influenced by the surface area and surface
activity of the electrode. To suppress the hydrogen evolu-
tion, the specific area must be sufficiently low without
sacrificing too much capacitance. In addition, the surface
activity of the carbon materials can be effectively tuned by
heteroatom doping (such as N, B, S and P), thus resulting in
the inhibition of the HERs and better cycling performances.
(2) Adding hydrogen evolution inhibitors. Adding hydro-
gen evolution inhibition additives to carbon materials has
been proved to be an effective way to inhibit the hydrogen
evolution reactions, as the introduction of inhibitors may
increase the hydrogen overvoltage.
However, the underlying mechanism of HER on carbon
materials is still unclear and needs further investigation.
Gaining the fundamental physical and chemical insights into
hydrogen evolution and inhibition, especially developing the
advanced carbon materials and inhibitors, offers the possi-
bility of significantly improving battery performances.
Acknowledgments This work was supported by the Science and
Technology Program of State Grid Corporation of China and the
National Thousand Talents Program of China.
Conflict of interest The authors declare that they have no conflict
of interest.
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