Ionics

https://doi.org/10.1007/s11581-018-2450-5

REVIEW

Review on the roles of carbon materials in lead-carbon batteries

ZhenDong Hao 1 & XiaoLong Xu 1 & Hao Wang 1 & JingBing Liu 1 & Hui Yan 1

Received: 11 December 2017 / Revised: 3 January 2018 / Accepted: 10 January 2018

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Lead-acid battery (LAB) has been in widespread use for many years due to its mature technology, abound raw materials, low cost,
high safety, and high efficiency of recycling. However, the irreversible sulfation in the negative electrode becomes one of the key
issues for its further development and application. Lead-carbon battery (LCB) is evolved from LAB by adding different kinds of
carbon materials in the negative electrode, and it has effectively suppressed the problem of negative irreversible sulfation of
traditional LAB. Different carbon materials play different roles in LCB, including construction of conductive network, double-
layer capacitance storage effect, formation of porous structure and steric effect. Moreover, research on composite material
additives (such as Pb-C composite materials and polymer-C composite materials) and Pb-C composite electrode have become
a research focus in the past few years; it has been another effective way to improve the performance of the negative electrode. On
the other hand, due to the relatively low overpotential of carbon materials, the hydrogen evolution reaction (HER) will be
aggravated in LCB, which affects its electrochemical performance. It is necessary to modify carbon additives or add other
additives to inhibit the HER. This paper will attempt to summarize the roles of carbon additives in the negative electrode made
by previous research and illustrate the effect of composite material additives and Pb-C composite electrode on the negative
electrode. Moreover, we will also sum up the method for solving the HER by reviewing previous research.

Keywords Lead-carbon battery . High-rate partial-state-of-charge . Irreversible sulfation . Carbon material . Hydrogen evolution

Introduction technology, abundant raw material, low cost, high safety,

In the twenty-first century, resource shortage and energy crisis
have become increasingly prominent, which forces people to
make full use of existing energy including wind, water, and
solar. However, as these energy sources are usually unstable, it
is necessary to find some stable energy storage system.
Electrical energy storage devices with high stability have been
extensively studied these years, and these devices include
lead-acid batteries, lithium-ion batteries, nickel-metal hydride
batteries, and supercapacitors [1–5].
Among these candidates, lead-acid battery (LAB) was
invented in the nineteenth century, and this kind of energy
storage device is widely used in the world for the past few
decades [6–9]. The advantages of LAB include mature
* Hao Wang
haowang@bjut.edu.cn
1
The College of Materials Science and Engineering, Beijing
University of Technology, Beijing 100124, China
and high efficiency of recycling, and thus, it is used in a wide
range of automobile applications for SLI (engine starting,
lighting, and ignition), UPS (uninterrupted power supply),
and energy storage system [10–20].
The usage amount of LAB has become the largest among
the secondary batteries. According to a recent report, the glob-
al production value of LAB accounted for about 68% of the
total value of secondary batteries in recent years [21]. When
applied in automobiles, railways, and communications, LAB
is more competitive than other candidates [22]. After a more
than a decade of rapid development, China has the largest
LAB industry worldwide [23, 24]. For the past few years in
China, the application of LAB has been increased by the quick
development of auto, transportation, grid storage, and tele-
communication industries [25, 26]. Besides, extensive use of
conventional internal combustion engine vehicles worldwide
has brought some negative effect like the high CO2 emission
and global warming, which promotes the development of
electric vehicle (EV) and hybrid electric vehicles (HEVs).
As one of the candidate for HEV, the performances of LAB
need to be enhanced continuously by applying some new

technology [27–32]. In the next few years, research on im-
proving the performance of LAB is of great importance in
order to meet future needs.
Electrochemical principles of LAB
and the irreversible sulfation in negative
plates
Electrochemical principles of LAB
The active materials of the LAB are PbO2, Pb, H2O, and
H2SO4, among which PbO2 and Pb are positive active mate-
rial (PAM) and negative active material (NAM), respectively.
H2SO4 solution is the electrolyte. PbO2 in the positive elec-
trode and Pb in the negative electrode are electrochemically
active. The two electrode active materials are formed by many
kinds of mixtures of bivalent lead compounds through forma-
tion process [13]. Chemical reactions occurring during the
charge and discharge process of LAB are as follows:
Positive electrode
Charge : PbSO4 þ 2H2 O−2e− ¼ PbO2 þ 4Hþ þ SO2−
4 to the charge process, and thus, the charge acceptance of the
Discharge : PbO2 þ 2e− þ SO2− þ negative electrode and the charge efficiency of the battery will
4 þ 4H ¼ PbSO4 þ 2H2 O
Negative electrode
Charge : PbSO4 þ 2e− ¼ Pb þ SO2−
4
Discharge : Pb−2e− þ SO2−
4 ¼ PbSO4
Total reaction
Charge : 2PbSO4 þ 2H2 O ¼ PbO2 þ 2H2 SO4 þ Pb
Discharge : PbO2 þ 2H2 SO4 þ Pb ¼ 2PbSO4 þ 2H2 O
As is shown above, the electrochemical principle of LAB is
mainly dependent on the reversible conversion of PbO2 and
Pb. During the discharge process, PbO2 in the positive elec-
trode will accept electrons given by Pb in the negative elec-
trode and PbSO4 will formed on both electrodes. When the
battery is charged, PbSO4 will be electrochemically converted
to PbO2 and Pb at positive electrode and negative electrode,
respectively. Meanwhile, SO2− 4 will flow into the electrolyte
solution and form H2SO4 [33, 34].
The irreversible sulfation in negative plates
Theoretically, the charge and discharge process are reversible.
But when the battery is operated practically, different issues
will occur on both electrodes. The failure modes of the posi-
tive electrode include positive grid corrosion and softening
and degradation of PAM. On the negative electrode, irrevers-
ible sulfation and hydrogen evolution are the major problem,
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which will be introduced in the following section. In addition,
other failure modes will also do harm to the battery, such as
water loss, internal short circuit, and electrolyte stratification
[35–38].
When LAB is used for HEV, the battery needs to be
charged and discharged at high rates, and this kind of appli-
cation requires the battery to work under partial-state-of-
charge (PSoC), which is termed high-rate partial-state-of-
charge (HRPSoC) cycling [31, 39]. When the battery is oper-
ated under HRPSoC, it provides advantageous conditions for
the recrystallization process of PbSO4, which leads the small
PbSO4 microcrystals dissolve and participate onto the big
PbSO4 crystals which have low solubility [40]. The above
phenomenon will eventually lead to the progressive accumu-
lation of PbSO4 mainly on the surface of the negative elec-
trode [41]. When the battery is charged, the large PbSO4 crys-
tals on the surface of the electrode are not able to effectively
convert to Pb. The above phenomenon is called the irrevers-
ible sulfation. Under HRPSoC cycling, the big PbSO4 crystals
grow further, leading eventually to progressive sulfation of the
negative electrode. Unreduced PbSO4 will participate onto the
surface of Pb phase, which will limit the latter’s contribution
be greatly reduced [11, 42, 43]. These problems will eventu-
ally lead to the battery failure and limit the wider application
of the battery.
Mechanism of carbon materials
of lead-carbon battery
For solving the problem of irreversible sulfation of the nega-
tive electrode and improve the electrochemical performance
of LAB, people have done a lot of research in recent years and
one main way is related to the appearance of lead-carbon
battery (LCB), which adds carbon material to the negative
electrode of LAB, such as graphite, carbon black (CB), acti-
vated carbon (AC), carbon nanotubes, or the mixture of them
[8, 44]. Carbon nanomaterials have been widely used in ener-
gy storage and conversion, including secondary batteries, fuel
cells, and pseudocapacitors [39, 45]. Carbon nanomaterials
have excellent properties such as large specific surface area,
superior conductivity, and excellent chemical stability [46,
47]. Many types of carbon nanomaterials have been widely
used in battery systems, including lithium-sulfur battery,
lithium-ion battery, and supercapacitor [48–65]. Meanwhile,
carbon materials, especially carbon nanomaterials, have been
extensively applied to LAB in the past few decades.
Different types of carbon material additives have different
effects on the negative electrode of LAB. For instance,
Logeshkumar et al. studied the effect of some nanostructured
additives on the performance of the negative electrode [66];
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the charge-discharge of the battery with different negative
carbon additives indicated that the performance was enhanced
to varying degrees when compared with no additives (shown
in Fig. 1). The results suggested that the maximum specific
capacity improvement was gained by adding MWNT
(multiwalled carbon nanotube), and the capacity was im-
proved following the next order: MWNT > graphene >
Vulcan XC-72 carbon > fullerene > no additives. In this paper,
we summarized the different effects of carbon material addi-
tives, including construction of conductive network, double-
layer capacitance storage effect, formation of porous structure,
and steric effect.
Construction of conductive network
When the dense and non-conductive PbSO4 crystals are
formed on the negative plate during the discharge process,
the utilization of active materials will be reduced, and
thus, the conductivity of the NAM will be reduced [67].
From this point of view, one way to inhibit the irrevers-
ible sulfation is to enhance the conductivity of the NAM.
Many kinds of carbon materials can construct conductive
network in the negative electrode, which will promote the
transformation of PbSO4 to Pb by enhancing the electron-
ic conductivity.
Different amount of carbon was added to the negative
plates of LAB by Shiomi et al. [68]. The results showed
that the addition of increasing amounts of carbon in the
negative plates suppressed the accumulation of PbSO4
effectively, and the cycle life of LAB was also improved,
especially when LAB was operated in PSoC conditions.
They found that these positive results were due to the
Fig. 1 The effect of different
carbon additives on the
electrochemical performance of
LCB (Vulcan XC 72 Vulcan XC
72 carbon, MWNT multiwalled
carbon nanotube) [66].
Reproduced from [66] with
permission from Elsevier
conductive network of carbon particles formed on
PbSO4 particles and the conductive network helped to
improve the rechargeability of PbSO4 in the negative
plates of LAB.
Multiwalled carbon nanotubes (MWCNTs) have been used
as carbon material additives of LAB by Saravanan et al. [69].
MWCNTs were observed to be connected with active mass
particles, and all particles were interlaced together to form a
network wiring in the NAM, and thus, an effective network
percolation was formed, which is shown in Fig. 2a, b. The
active material utilization and the cycle life of the LABs with
MWCNTs as negative carbon material additives showed sig-
nificantly enhanced electrochemical performance, which was
due to the significant specific electroactive area formed by
MWCNT conductive network within the NAM. The accumu-
lation of PbSO4 crystal was suppressed in most areas of the
negative electrode.
Graphene nanosheets (GNs) with large specific surface
area, excellent flexibility, and high conductivity were
added to the negative plate by Li et al. [70]. Under
HRPSoC conductions, the cycle life of LAB was en-
hanced (more than 370%) and the utilization ratio of
NAM was also gone up. The improved performance was
due to the 3D conductive framework constructed by the
GNs. During charge and discharge process, the continu-
ous conductive network can provide fast electron transfer
for electrochemical deposition (Pb2+/Pb) and electrochem-
ical dissolution (Pb/Pb2+). Under HRPSoC conditions cy-
cle, the continuous conductive network can provide suffi-
cient H+ and HSO−4 ions for chemical dissolution (PbSO4/
Pb2+) and chemical deposition (Pb2+/PbSO4), and thus,
the irreversible sulfation was inhibited significantly.

Fig. 2 a, b The NAM with
MWCNTs as additives. The inset
in b is an enlarged SEM images
(after 70 charge/discharge cycles)
[69]. Reproduced from [69] with
permission from ECS
Double-layer capacitance storage effect
Supercapacitor is a kind of energy storage system, and it owns
numerous advantages including high power density, fast re-
charge capability, and long lifespan [71–74]. AC typically has
large capacitance, and it is widely used as negative electrode
material of supercapacitor due to its high surface area and
relatively good electrical conductivity [75, 76]. In LAB, some
kinds of carbon materials can cause supercapacitor effect in
the negative electrode. A large number of micropores and
mesopores existed in AC, and these pores constitute plenty
of small capacitors. When the battery is charged during
HRPSoC conditions, these small capacitors could absorb
charge current and then release part of the current to promote
the conversion of PbSO4 to Pb. In the subsequent discharge
process, the absorbed charge current can be released, which
will enhance the high rate performance of the battery [44, 77].
Five different carbon materials and two lignosulfonates
were added to the negative plate of LAB by Blecua et al.
[78]. The specific surface area and mean particle size of these
carbon materials were different. They found that the charge
acceptance of the negative plate was enhanced by adding
these carbon materials. The cycle life under PSoC was also
improved by reducing the process of irreversible sulfation.
They came to the conclusion that these carbon materials acted
as supercapacitors during charging process. During this pro-
cess, electrical charges could be concentrated inside the po-
rous structure of these carbon materials, which resulted in the
decrease of ohmic resistance in the entire negative plate and
the increase of the charge acceptance ability [78, 79].
Xiang et al. mentioned capacitance effect in their research
of the effects of activated carbon additives on the performance
of the negative electrode of LAB [44]. The result of their study
suggested that activated carbon with large BET (Brunauer-
Emmett-Teller) surface area can form large area of electric
double layer. During high-rate charge and discharge process,
the electric double layer could store protons and electrons
rapidly. When the battery is operated under HRPSoC cycling,
the activated carbon is able to absorb a large proportion of the
transient current during the charge process and release elec-
trons when the charge process is finished. The schematic
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illustration of capacitance effect is shown in Fig. 3. This ad-
vantageous effect of activated carbon can largely promote the
electrochemical conversion of the NAM at high rate.
Pavlov et al. researched the influence of carbon on the
negative electrode of LAB [79]. They found that some acti-
vated carbon with micron-sized particles process high affinity
to Pb. These particles can get integrated into the Pb skeleton
and form a lead-carbon active mass with Pb. The activated
carbon they studied had high surface area and microporous
structure and the carbon could play the role of supercapacitors
when water entered into their pores. Electric charges could be
concentrated in these small supercapacitors during charge pro-
cess. Thus, the charge acceptance of the negative electrode
will be enhanced and the process of irreversible sulfation will
be slowed down.
Fernández et al. added activated carbon and expanded
graphite with different specific surface area into the negative
plate [80]. They found that carbon with high specific surface
area could cause high values of charge acceptance power and
enhanced cycle life, and thus, the process of irreversible
sulfation was largely slowed down. The most likely working
mechanism would be the supercapacitor effect. When carbon
materials with pretty high surface area is used as negative
additive, such as AC with the specific surface area of 200–
2000 m2 g−1, they can result in the supercapacitor effect, and
thus, a fairly high capacitance values can be provided.
Formation of porous structure
When the battery is operated under HRPSoC, the strong and
compact layer of PbSO4 will form on the surface of the neg-
ative plate, which makes it difficult for the electrolyte to come
into the internal structure of the negative plate, and thus, the
charge and discharge efficiency of the battery will be greatly
reduced [80, 81]. Therefore, another way to solve the problem
of irreversible sulfation is to generate loose and porous struc-
ture in NAM of LAB, which will allow the electrolyte to enter
the internal structure of NAM easily, and thus, most of the
NAM can participate in the charge process, and the transfor-
mation of PbSO4 to Pb will be promoted.
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Fig. 3 The schematic illustration of capacitance effect. a Initial stage of charge. b Steady stage of charge. c The stage after charge [44]. Reproduced from
[44] with permission from Elsevier
Graphene was added as a negative additive for valve-
regulated lead-acid (VRLA) batteries by Zhu et al. [82]. The
results showed that the charge cutoff voltage was remarkably
reduced and the discharge cutoff voltage was increased in
HRPSoC cycling (Fig. 4a, b). Batteries with better charge
acceptance would present higher discharge cutoff voltage,
which will eventually lead to the increase of the cycle life
under HRPSoC conditions (about 13,000 cycles). Moreover,
the negative plate without adding graphene was composed of
some relatively smooth and big PbSO4 particles while the
negative plate adding graphene consisted of some relatively
loose and small PbSO4. The reason for gaining the enhanced
performance was that the porosity of graphene could provide
abundant acid reservoirs in the interior of negative plates, and
these acid reservoirs could bring active sites for the migration
of PbSO4 during discharge process [83]. Therefore, the con-
version of PbSO4 to Pb in the charge process was promoted
and the recrystallization during cycling was inhibited.
AC materials were added to the negative electrode in the
study of Xiang et al. [44]. The HRPSoC cycle life and the charge
acceptance of the LAB was improved by adding 2 wt.% AC
with tens of micron in diameter (AC2). One of the reasons for
Fig. 4 The charge/discharge cutoff voltage of a the batteries without adding graphene and b the battery adding graphene during HRPSoC cycling [82].
Reproduced from [82] with permission from ESG
gaining the enhanced electrochemical performance was called
the electrolyte-supplying effect. The schematic diagram of the
effect is shown in Fig. 5. AC2 exhibited high pore volume
(1.662 cm3 g−1) and mean porous of 2 nm approximately. On
the other hand, the radii of H3O+ and HSO−4 was normally
regarded as about 200–400 pm, which means the porous of
AC2 could act as the accommodation of H2SO4. AC2 could
provide sufficient H+ and HSO−4 in the interior of the negative
electrode, and thus, the reaction could occur in the internal of the
negative plate instead of stopping on the surface during high rate
discharge. PbSO4 could form in the entire cross section of the
negative plane, and the relative density of H2SO4 was low after
discharge, which was favorable for the dissolution of PbSO4,
thereby forming Pb2+ and SO2− 4 .
Swogger et al. added discrete carbon nanotubes (dCNTs) to
the negative plates of the LAB [84]. During the mixing pro-
cess, dCNT were uniformly dispersed into the battery pastes
and they have no influence on the paste rheology, density, or
consistency. SEM images (Fig. 6) showed that the structures
of the negative plates were tight and well-defined. The results
suggested that the addition of dCNT plays a role in the poros-
ity of the negative plate. When the porosity of the negative

Fig. 5 The schematic illustration
of the electrolyte-supplying effect
[44]. Reproduced from [44] with
permission from Elsevier
plate increases, the electrolyte can get access to previously
unreachable areas of the negative plate, and thus, the utiliza-
tion of the active materials will be enhanced.
Steric effect
Although the pores in the negative electrode could promote
the electrolyte into the internal structure of NAM easily, when
the pores are much larger, big PbSO4 may grow in these large
pores. The conversion efficiency of PbSO4 to Pb will be re-
duced when the particle size of PbSO4 crystals in NAM is
micron level. In general, the specific surface area of the pos-
itive plate is much larger than the negative plate, which means
the pore size of the negative plate is much bigger than the
positive plate, and thus, there is more room for the growth of
PbSO4 in negative plate [77, 85, 86]. The steric effect is
Fig. 6 a The microstructure of the
negative paste without dCNT. b
The microstructure of the
negative paste with dCNT [84].
Reproduced from [84] with
permission from Elsevier
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considered to be another effective way to solve the irreversible
sulfation in the negative plate. Some kinds of carbon materials
like expanded graphite can separate the growth of PbSO4 [87].
The above description is the main principle of the steric effect.
Micka et al. compared the effects of some negative addi-
tives on the cycle life of LAB; these additives include pow-
dered graphite, purified flake graphite, carbon black, pow-
dered TiO2, multiwall carbon nanotubes, and glass fibers
[88]. The result showed that improving the cycle life of
LAB during PSoC cycling can be achieved not only by adding
some kinds of powdered carbon into the negative plate but
also by adding the powder of some inert materials. The reason
for the enhanced cycle life is mainly based on the steric hin-
drance of the growth of PbSO4 produced by these additives, so
the growth of PbSO4 is restrained and the cycle life of LAB
during PSoC is improved. Their study suggested that some
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powdered carbon materials and some powdered inert mate-
rials can inhibit the growth of PbSO4 crystals by the steric
effect [85, 86, 88].
Pavlov et al. pointed out that carbon additives could decrease
the mean pore radius of NAM, which is in favor of the forma-
tion of PbSO4 with small crystal size and high solubility [40,
89]. Then, in the subsequent charge process, there is adequate
Pb2+ to form Pb, and thus, the irreversible sulfation will be
slowed down and the cycle life of the battery will be enhanced.
Research of composite material additives
and Pb-C composite electrode in the negative
electrode
In the past few years, composite material additives (such as
Pb-C composite materials and polymer-C composite mate-
rials) and Pb-C composite electrode have become a research
focus. Compared with carbon additives, these composite ma-
terial additives and Pb-C composite material electrode can
overcome the shortcomings of carbon additives. Moreover,
these additives help to explore the intrinsic effect of carbon
additives in lead-carbon electrode. When applied in LAB, the
enhanced performance is mainly based on the special structure
or the synergy of the component of the composite material
additives.
A rice-husk-derived hierarchically porous carbon materials
with super large micrometer-sized pores on its surface (donat-
ed as RHC) was investigated by Zhang et al., and RHC was
used to prepare lead-carbon composite electrode [87]. The
result indicated that the composite electrode has good cycling
stability, stable capacity, and near 100 % coulombic efficiency
in PSoC test, which was due to the stable lead-carbon com-
posite structure formed during the formation and charge-
discharge process, the coarse surface, and the large pore with
size of micrometers of RHC promoted the formation of the
stable composite electrode, and thus, the electrode provided
large carbon surfaces for the electrolytic deposition of Pb on
its surface. The schematic illustration is shown in Fig. 7.
A hybrid carbon additive was prepared by Wang et al. to
inhibit the irreversible sulfation and improve the cycle perfor-
mance of LCB [90]. The additive consisted of lead-doped
porous carbon composite and conductive graphite with differ-
ent mass ratios. By studying the synergistic action, it was
found that this kind of hybrid carbon additive showed a
unique structure of sheets attached to porous bulk, which
could not only make the nano-Pb particles electrodeposited
into carbon pores but also confine the Pb particles on the
external surface of carbon between sheets graphite and porous
carbon bulk (Fig. 8). When adding 1% of the hybrid additives
with the mass ratio of conductive graphite and lead-doped
porous carbon composite was 3:7 to the negative plate, the
battery showed the best cycle performance (Fig. 8). In this
way, the irreversible sulfation was largely inhibited.
In the research of Yang et al., the composites of polypyrrole
(ppy) and graphene oxide (GO) were selected as additives of
the negative plate [91]. The results showed that the composite
additives could enhance the HRPSoC cycle performance of
the battery. They found that the composites could increase the
BET surface area and total pore value, which was beneficial to
the formation of extra nucleation sites for PbSO4 crystals and
the small-sized PbSO4 crystals with high solubility could be
formed. In addition, the composites possessed large specific
capacitance, and thus, the formation of irreversible PbSO4
crystals was prevented by the strong buffer function for large
charging/discharging currents. In this way, the irreversible
sulfation was inhibited significantly.
Lead (II)-containing active carbon (Pb@C) was prepared
by Tong et al., and it was added to the negative plate [92].
They found that the lead(II) ions distributed homogeneously
in the carbon bulk of the Pb@C materials. When it was added
to the negative plate, the NAM utilization was improved and
the cycle life and charge acceptance under HRPSoC condi-
tions were also enhanced. When the batteries were
disassembled, they found that Pb@C materials had high affin-
ity to Pb and the porous-skeleton structure was formed. The
structure could increase the porosity of the negative plate,
which was in favor of the diffusion of electrolyte and thus,
the dissolution of PbSO4 was facilitated. Figure 9 shows the
working mechanism of the Pb@C materials.
Methods for solving the problem of hydrogen
evolution in lead-carbon battery
It can be seen that carbon additives played a crucial role in
enhancing the performance of LAB during HRPSoC condi-
tion. On the other hand, carbon additives may bring some
negative problems such as capacity decrease and the hydrogen
evolution reaction (HER). The HER means when the battery is
under the state of overcharge, H+ in the electrolyte near the
negative electrode is electronically reduced to hydrogen atoms
and combined into hydrogen. The hydrogen evolution
overpotential of carbon materials is relatively low [93].
When LCB is operated under HRPSoC conditions, serious
HER will be introduced which will lead to the release of more
gas at the end of the charging process, even thermal run away
or even electrolyte dry-out, and thus [31, 92, 94–96], the cycle
life of the battery will be reduced.
The HER involves three possible steps, including Volmer
step, Heyrovsky step, and Tafel step. These possible steps are
strongly dependent on the physical, chemical, and electro-
chemical properties of the electrode surface. Moreover, these
possible steps can be simply determined by evaluating the
Tafel slope from the HER polarization curve [97].

Fig. 7 The schematic illustration
of the role of RHC in the lead-
carbon composite electrode [87].
Reproduced from [87] with per-
mission from Elsevier
Researchers have done a lot of work to inhibit the HER,
which was mainly based on enhancing the overpotential of the
HER and reducing the hydrogen evolution current. Moreover,
Trasatti et al. demonstrated the BVolcano plots,^ which de-
scribed the exchange current density of the elements for the
HER in acid to calculate the metal-hydrogen bond strength.
These volcano relations state that the materials with extremely
low or extremely high bond strength of metal-hydrogen can
result in slow kinetics for HER-Pb [98]. The selection of the
HER inhibition agents should mainly base on the above con-
clusion. The following text summarizes the research progress
of inhibiting the HER in recent years.
Adding Pb-C composite material
Nano-lead-doped active carbon (nano-Pb/AC) composite
was prepared using ultrasonic-absorption and chemical-
precipitate method by Hong et al. [96]. They mentioned
that when the potential is lower than the onset potential
Fig. 8 The cycle performance of
the battery with different additives
and the schematic illustration of
synergistic action mechanism by
adding the hybrid carbon additive
[90]. Reproduced from [90] with
permission from Elsevier
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of hydrogen evolution, hydrogen evolution current in-
creases exponentially with the potential negatively
shifted. The onset potential of hydrogen evolution of
nano-Pb/AC electrode, AC and pure Pb are − 1.14, −
1.02, and − 1.23 V, respectively (Fig. 10). But the HER
current of the composite (− 8.07 mA cm−2) was only
16% of AC (− 50.59 mA cm−2) at − 1.36 V (Fig. 10).
They explained that the nano-Pb composite absorbs on
the surface of the AC pores, which may increase the
adsorption impedance of hydrogen. Moreover, the com-
posite could change the structure of Pb paste and im-
prove the migration of ions significantly. The 3-h rate
capacity, quick charging performance, high current
discharging performance, and cycling performance of
the battery that added with nano-Pb/AC were all en-
hanced distinctly compared with the battery added with
AC. Their research suggested that this kind of nano-Pb/
AC composite material is appropriate for application in
LCB to improve its performance.
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Fig. 9 The schematic diagram for

the working mechanism of Pb@C
materials [92]. Reproduced from
[92] with permission from
Elsevier

Wang et al. used a mesopore-dominated porous carbon
(MC) to be the Pb electrodeposition substrate and prepared
Pb-doped mesopore-dominated porous carbon (Pb@MC)
composite by vacuum impregnation followed by chemical-
precipitation method [99]. By using the electrochemical mea-
sures with a three-electrode system, they found that the HER
was significantly slowed down, which is shown in Fig. 11.
Their results showed that the mesopore-dominated structure
of MC materials was beneficial for the Pb electrodeposition on
the internal surface of pores. After the Pb electrodeposition,
they found that the Pb particles on the external surface of MC
could become smaller while more quantity. Moreover, the Pb
particles on the external surface of carbon could not only
electrodeposit into the pores in the form of nanoparticle but
also attached on the pore wall with atomic state through long
cycle testing. The Pb electrodeposited on the surface of carbon
could inhibit the hydrogen evolution effectively.
Heteroatom doping
Phosphorus-doped activated carbon (P-AC) which exhibited
prominent inhibition for the HER was prepared by Wang et al.
[93]. At 1.35 V vs. Hg/Hg2SO4, the HER current density of
AC was about 17 times larger than that of P-AC. Meanwhile,
the HER onset potential of P-AC (− 1.21 V) was more nega-
tive than that of AC (− 0.97 V). They explained that the phos-
phorus is bonded with carbon covalently, creating a negative
charge on the adjacent carbon atoms, which can accelerate the
formation of absorbed hydrogen, making it more difficult for
the desorption process of H+, and thus, the HER on the carbon

Fig. 10 Linear sweep

voltammetry (LSV) curves of
different electrode [96].
Reproduced from [96] with per-
mission from Elsevier

Fig. 11 CV curves of samples before cycle testing, a − 0.7 to − 1.5 V,
1 mV s−1, b 0 to − 1.2 V, 0.7 mV s−1. c High-rate cycling performance of
MC and Pb@MC after Pb electrodeposition. CV curves after cycle
surface will be inhibited significantly. The adsorption energies
of H+ on P-AC are much higher than that of AC at different
corresponding sites (Fig. 12). What is more, the cycle perfor-
mance of the battery added with P-AC was quite better than
the battery added with AC, which proves that P-AC is a prom-
ising candidate of negative additive for LCB.
Hong et al. presented a new way to inhibit the HER for
LAB by preparing nitrogen group-enriched AC (NAC) [98].
The results manifested that the HER current of NAC was only
12% of the original AC. The electronegativity of nitrogen
atom is stronger than that of carbon. When nitrogen atoms
are doped in carbon matrix, the electrons of the neighboring
and/or further carbon atoms will be attracted by nitrogen
atoms, which will lead carbon atoms electron deficient and
weaken the bond strength to hydrogen. Based on the above
process, the HER is inhibited significantly. Furthermore, the
NAC also showed better capacity performance in LAB than
that of AC, which indicates that NAC has potential when
applied in LAB.
Adding oxidizing material
Zhao et al. found that electrochemically active carbon (EAC)
can effectively restrain the sulfation of the negative plate
[100]. On the other hand, it will cause the HER significantly.
In their research, Ga and Bi was applied which possess high
hydrogen evolution overpotential. They added Ga2O3 and
Bi2O3 into the EAC. The result showed that the cutoff
Ionics
testing, d − 0.7 to − 1.5 V, 1 mV s−1, e 0 to − 1.2 V, 0.7 mV s−1 [99].
Reproduced from [99] with permission from Elsevier
charging voltage was decreased and the cutoff discharging
voltage was increased under HRPSoC conditions when added
a certain amount of Ga2O3 and Bi2O3 into the negative plate.
The HER was inhibited distinctly when added Ga2O3 and
Bi2O3 into EAC.
Similarly, In2O3 is a kind of high hydrogen evolution
overpotential material as well. Zhao et al. found that EAC with
an appropriate addition of In 2 O 3 could increase the
overpotential of hydrogen evolution effectively and promote
the conversion of PbSO4 to Pb [101]. Moreover, the HRPSoC
cycle life was also enhanced.
Bi2O2CO3 modified AC composite was successfully pre-
pared using hydrothermal method by Lian et al. [102]. When
adding 4 wt% of the composite to the negative electrode, the
hydrogen evolution current was suppressed by 93.1% and the
overpotential of HER was increased by 230 mV compared
with pristine AC additives. Moreover, the cycle performance
of LAB was significantly enhanced by adding the composite.
These excellent performances were due to the uniform distri-
bution and strong interaction between AC and Bi2O2CO3 in
the composite.
Conclusion and perspective
This paper reviewed the roles of carbon materials in the neg-
ative electrode of LCB. As mentioned earlier in this paper, we
can conclude that carbon materials play a key role in inhibiting
Ionics
Fig. 12 Optimized geometric
structures and adsorption energies
of H+ at different corresponding
sites on a–c AC and d–f P-AC
[93]. Reproduced from [93] with
permission from the Royal
Society of Chemistry
the irreversible sulfation of LAB. The roles of carbon addi-
tives mainly include the following four aspects:
1. Construction of conductive network: The conductive net-
work can enhance the conductivity of NAM and promote
the conversion of PbSO4 and Pb.
2. Double-layer capacitance storage effect: Micropores and
mesopores existed in some kinds of carbon materials and
these pores can constitute plenty of small capacitors. These
small capacitors can absorb charge current during HRPSoC
conditions and release part of the current to promote the
conversion of PbSO4 to Pb. Moreover, the absorbed charge
current can be released to enhance the high rate perfor-
mance of the battery in the subsequent discharge process.
3. Formation of porous structure: The pore structure in car-
bon materials can allow the electrolyte to enter the internal
structure of NAM easily and promote more of the NAM
to participate in the charge process.
4. Steric effect: Some kinds of carbon materials can separate
the growth of PbSO4, and others can limit the growth
space of PbSO4 owning to their relatively small pore size.
Moreover, composite material additives (such as Pb-C
composite materials and polymer-C composite materials)
and Pb-C composite electrode have become a research focus.
They have a positive effect on inhibiting the irreversible
sulfation and enhancing the performance of LAB, which is
mainly due to the special structure or the synergy of the com-
ponent of the composite material additives. Thus, it is still
necessary to go on studying the carbon materials for LAB.
On the other hand, the hydrogen evolution overpotential of
carbon materials is relatively low, which will introduce severe
HER to the battery. Some solutions have been made by per-
vious research, including adding composite material, hetero-
atom doping, and adding oxidizing material. Carbon additives
will function better when the HER is significantly inhibited; it
will promote the development of LCB, such as when LCB
apply in automobile (EV or HEV) and use under HRPSoC
conditions.
In short, LAB, especially LCB, will play a significant role
in the energy storage field and it will account for a large share
in the battery market in the future [13]. Firstly, carbon mate-
rials with high specific surface area, good conductivity, and

good affinity with Pb will become the research focus of the
negative additives of LCB in future. Moreover, composite
material additives with superior performance will be another
research hotspot to inhibit the irreversible sulfation and the
HER in LCB.
Acknowledgements This work is supported by the Scientific and
Technological Development Project of the Beijing Education
Committee (No. KZ201710005009).
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