Journal of Energy Storage 18 (2018) 414–420

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Journal of Energy Storage

journal homepage: www.elsevier.com/locate/est

Effect of graphene oxide with different oxygenated groups on the high-rate T

partial-state-of-charge performance of lead-acid batteries
⁎
Weijia Caia, Kai Qia, Zhenyu Chena,c, Xingpeng Guoa,c,d, Yubing Qiua,b,
a
School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, PR China
b
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of Education, PR China
c
Hubei Key Laboratory of Materials Chemistry and Service Failure, Wuhan, 430074, PR China
d
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou, 510006, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Four graphene oxide samples with different oxygenated groups are prepared and characterized, and then em-
Lead-acid battery ployed as the additives in the negative active materials to investigate the effect of different oxygenated groups of
High-rate partial-state-of-charge graphene oxide on the H2 evolution performance of negative plates and the high-rate partial-state-of-charge
Graphene oxide cycle life of simulated lead-acid batteries. The results indicate that the H2 evolution and the reduction of PbSO4
Oxygenated groups
processes are largely accelerated by the graphene oxide additives. An increase in CeO groups (CeOH and
Hydrogen evolution performance
CeOeC) of graphene oxide can largely promote the H2 evolution process. The addition of the graphene oxide
additives largely increases the surface area and total pore volume of the negative plates, meanwhile obviously
increases the hydrophilicity of negative active materials to facilitate the diffusion of acid into the inner of the
plate. The high-rate partial-state-of-charge cycle life of the simulated test cells containing the graphene oxide
samples is prolonged significantly, and especially those containing graphene oxide with less CeO groups and
more carbonyl and carboxyl groups have the longest cycle life, which seems to be more appropriate as the
additive of negative plates.

1. Introduction
Working under conditions of high-rate partial-state-of-charge
(HRPSoC) continuously, lead-acid batteries will suffer quick battery
failures owing to the irreversible sulfation of negative plates [1,2]. In
recent years, various carbon materials, including carbon black (CB)
[3–5], activated carbon (AC) [6–10], graphite [11,12], carbon nano-
tube [13–16], graphene [17–19], etc., were directly introduced into the
negative active materials (NAM) to prevent the progressive sulfation of
negative plates and significantly prolong the HRPSoC cycle life of lead-
acid batteries [20]. However, these lead-carbon batteries suffer serious
hydrogen evolution to dry out their electrolyte quickly [21].
In order to overcome this H2 evolution problem, the carbon mate-
rials were modified with various methods [6,7,22], e.g. the modifica-
tion of their surface functional groups [8], the development of metals
(or metal oxides)/carbon materials composites [9,10,23] and the
combination of these two methods [24]. It was reported that acidic
surface functional groups of AC could promote the H2 evolution in
negative plates, while those alkaline surface functional groups could
inhibit it [8]. We also found that the surface functional groups of CB in
PbO/CB composites displayed the similar effect [24]. Different surface
functional groups of carbon materials may play an important role in
their H2 inhibition performance.
Based on our previous work [25], adding graphene oxide (GO) in
negative plates can significantly prolong the HRPSoC cycle life of lead-
acid batteries, however, also promote the H2 evolution in the negative
plate obviously. According to the effect of functional groups of AC and
CB, different oxygenated groups of GO may produce a different effect
on the H2 evolution process. But few studies have focused on this. In
this paper, GO with different oxygenated groups were prepared and
characterized, and then their influence on the H2 evolution ability of
negative plates and on the HRPSoC cycle life of simulated test cells was
investigated to identify the detailed effect of different oxygenated
groups of GO. The results of this work may benefit the selection of
appropriate GO for the further modification of its functional groups or
the preparation of metals (metal oxides)/GO composites for lead-acid
batteries.

⁎
Corresponding author at: School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, PR China.
E-mail addresses: caiwj_yuke@163.com (W. Cai), qikai@hust.edu.cn (K. Qi), chenzhenyu@mail.hust.edu.cn (Z. Chen), guoxp@mail.hust.edu.cn (X. Guo),
qiuyubin@mail.hust.edu.cn (Y. Qiu).

https://doi.org/10.1016/j.est.2018.06.004
Received 23 March 2018; Received in revised form 7 June 2018; Accepted 7 June 2018
2352-152X/ © 2018 Elsevier Ltd. All rights reserved.
W. Cai et al. Journal of Energy Storage 18 (2018) 414–420

Table 1 respectively, and those without GO are blank plates. A prepared ne-
Content of the materials used in negative pastes (wt. %, versus the lead oxide). gative plate (1.0 × 1.5 cm2) and two commercial positive plates
Acetylene Short BaSO4 Humic H2SO4* H2O GO (2.8 × 2.8 cm2) were separated with a glass mat (AGM, thick-
black fibers Acids samples ness = 2 mm) separator, and then 65 mL H2SO4 (1.28 g cm−3) was
added to form a flooded simulated lead-acid test cell [25].
Blank 0.2 0.05 0.4 0.7 12.5 10 0
GO added 0.2 0.05 0.4 0.7 12.5 13 - 15 1.0

* Density = 1.25 g cm−3. 2.3. Electrochemical measurements and HRPSoC cycle tests

2. Experimental The cathodic polarization curves of the prepared negative plates

2.1. Preparation of GO
A water-enhanced oxidation method, which belongs to a modified
Hummer’s method, was employed to prepare GO samples with different
species of oxygenated groups [26,27]. In an ice-bath (< 10 ℃), 1.0 g
graphite powder (99.95%, supplied by Qingdao Huatai, China) and
3.0 g KMnO4 were added in 46 mL concentrated H2SO4 with the dif-
0 the measured Peukert plots for the different kinds of simulated test cells
ferent initial addition of distilled water (V H 2O
= 0, 4 and 12 mL) and
were stirred continuously, then maintained at 40 ℃ for 2 h. According
0
to the different V H 2O
(0, 4 and 12 mL), the obtained GO is denoted as
GO1-M, GO2-M, GO3-M, respectively. The fourth GO sample was syn-
thesized in the system without the initial addition of distilled water
0
(V H 2O
= 0). But after the oxidation at 40 ℃ for 2 h, 100 mL distilled
water was slowly added into the reaction system and maintained at
90 ℃ for 15 min. The obtained GO is denoted as GO4-H [28]. After
centrifuging, washing by distilled water, and vacuum drying, the final
GO samples were prepared for the further test in this work. Except for
graphite powder, other reagents and chemicals used in this preparation
step were analytical grade (AR).
(Blank, GO-1, GO-2, GO-3 and GO-4) were measured in H2SO4
(1.28 g cm−3) at room temperature (25 ℃) using a GAMRY Reference
3000 electrochemical workstation. Two platinum electrodes and a Hg/
Hg2SO4 electrode were used as the counter electrode and the reference
electrode, respectively. The polarization potential range is from the
open circuit potential (EOCP) to −1.5 V vs. Hg/Hg2SO4 and the scan rate
is 1.0 mV s−1.
Before the HRPSoC cycle test, the 2C current was determined from
and the state-of-charge (SoC) of the test cells was discharged to 50%.
The schedule of the HRPSoC cycle test was: charge (2C, 30 s); rest
(10 s); discharge (2C, 30 s), rest (10 s). The limit of end-of-discharge
voltage (Vdischarge) and end-of-charge voltage (Vcharge) was 1.60 V and
3.0 V, respectively. After the first cycle-set test (2C-1 set), the second
(2C-2set) and the third cycle-set (2C-3set) test were conducted ac-
cording to the same procedures. All these tests were performed at room
temperature (25 ℃) and repeated at least three times.
2.4. Physical characterization

The as-prepared samples of GO1-M, GO2-M, GO3-M, and GO4-H

2.2. Preparation of negative plates and simulated test cells
Lead oxide power (oxidation degree = 82.6%) was supplied by a
commercial battery company. The content (versus the lead oxide) of
other materials in negative pastes is listed in Table 1, in which humic
acids (≥90%, Aladdin) and BaSO4 (AR) are reagents, and acetylene
black and short fibers are supplied from commercial battery companies.
The apparent density of the negative pastes was about 4.2 g cm−3,
which was adjusted by distilled water. The negative plate was prepared
using a Pb-Sn-Ca grid (1.0 × 1.5 cm2) and 1.0 g negative paste, and
then cured carefully and formed under a commercial formation pro-
cedure (H2SO4 density: 1.05 g cm−3; constant formation current:
8.5 mA g−1 and 17 mA·g−1; total charge delivered to NAM:
535.5 mAh g−1) [25]. The negative plates containing GO1-M, GO2-M,
GO3-M, and GO4-H are nominated as GO-1, GO-2, GO-3, and GO-4,
were characterized using X-ray diffraction (XRD, XRD-7000S, Japan)
with Cu Kα radiation, Fourier transform infrared spectroscopy (FTIR,
Vertex 70, Germany) in reflectance mode, and X-ray photoelectron
spectroscopy (XPS, VG Multilab 2000) analyses (the binding energies
were calibrated relative to the C 1 s peak from GO sample at 284.6 eV).
The morphology of the negative plates was observed using scanning
electron microscope (SEM, Nova NanoSEM 450, America). The specific
surface and porosity analysis for the negative plates, which had been
dried in vacuum at 120 ℃ for 2 h, was conducted using an ASAP2020 M
analyzer (America). The water contact angle of the prepared negative
plate was measured with a JC2000 contact-angle meter (Shanghai
Zhongchen Digital Technic Apparatus, China).

Fig. 1. (a) XRD patterns and (b) FTIR spectra of different GO samples.

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Fig. 2. XPS high-resolution spectra of C 1 s for (a) GO1-M, (b) GO2-M, (c) GO3-M, (d) GO4-H.

Table 2 increase in the contents of −OH and CeOeC on GO sheets. The in-
Relative contents of C–O, carbonyl, and carboxyl groups as well as the oxidation tensity ratio of the C]O (1725 cm−1)/H2O (1620 cm−1) peaks in GO1-
degree of the GO samples. M, GO2-M, and GO3-M is approximate, but much smaller than that in
Samples C 1s GO4-H. These results imply that GO4-H may have a higher content of
carbonyl groups (C]O) [27]. Apparently, the oxidation degree and
IC–O / ICC IC=O / ICC IO–C=O / ICC SCO / SC-Total (%) functional groups of different GO samples change with different
synthesis conditions.
GO1-M 1.42 0.17 0.06 57.14
GO2-M 1.89 0.19 0.05 63.81 Fig. 2 gives the XPS high-resolution spectra of C 1 s for the GO
GO3-M 2.18 0.22 0.05 65.16 samples, which consist of four types of carbon bonds: CeC/C = C
GO4-H 1.33 0.20 0.08 55.38 (284.6 eV, Peak 1), CeO (286.6 ± 0.1 eV, Peak 2), C]O (287.8 eV,
Peak 3), and OeC = O (289.0 eV, Peak 4) [26,34,35]. Table 2 lists the
peak intensity ratios of oxygenated carbon atoms (CeO, C]O, and
3. Results OeC = O) to intact carbons (CeC and C]C), i.e. IC–O/ICC, IC=O/ICC,
and IO–C=O/ICC, which generally demonstrate the relative contents of
3.1. Characterization of GO samples oxygenated carbon atoms. Also, the peak area ratio of oxygenated
carbon atoms (SCO) to the total C 1 s (SC–Total) in Table 2 reflects the
Fig. 1a shows the XRD patterns of different GO samples, in which oxidation degree of GO [24,25]. Among GO1-M, GO2-M and GO3-M,
the diffraction peaks of GO1-M, GO2-M, GO3-M, and GO4-H are mea- the content of CeO groups increases obviously (IC–O/ICC rises from 1.42
sured at 10.08°, 10.38°, 10.43° and 11.03°, respectively, while that of to 2.18) to improve the oxidation degree of GO (SCO/SC–Total rises from
graphite (2θ = 26.6°) is completely disappeared [29–31]. These results 57.14% to 65.16%), indicating that the hydroxyl and epoxy groups
indicate that the graphite structure is disassembled and GO sheets are (−OH and CeOeC) increase obviously with an increase in the initial
formed. The FTIR spectra in Fig. 1b show typical absorption peaks of addition of water content. For GO4-H, the content of CeO groups and
GO, including 1725 cm−1 (C]O), 1620 cm–1 (−OH bending modes in the oxidation degree are all the lowest (IC–O/ICC = 1.33 and SCO/
water molecules), 1395 cm−1 (−OH bending vibration in CeOH), SC–Total = 55.38%), but it has relatively higher carbonyl (C]O) and
1226 cm−1 (CeO) and 1055 cm−1 (CeOeC) [27,32,33]. The OeH carboxyl (OeC = O) contents [27]. These results further prove the
stretching vibrations in the region of 3600–3300 cm−1 correspond to above speculation from the FTIR analysis in Fig. 1b.
the hydroxyl and carboxyl groups of GO and residual water between GO
sheets [26]. Among GO1-M, GO2-M, and GO3-M, the absorption peaks
of −OH and CeOeC increase with an increase in V H 0
2O
, suggesting the

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were obtained from the results in Fig. 3 and the parallel experiments (at
least three times) to observe the effect of the GO additives [24,25],
including EH (H2 evolution potential), IEH (the current density of the
reduction of PbSO4 at EH ) and IH,-1.4V (the H2 evolution current density
at −1.4 V vs. Hg/Hg2SO4, which equals I-1.4V −IEH ). Table 3 lists the
average values and standard deviations of these characteristic para-
meters.
Compared with the characteristic parameters of the blank plate in
Table 3, all the EH values of the negative plates containing different GO
samples (GO-1∼ GO-4) become more positive, while their IEH and
IH,-1.4V values increase significantly. These results indicate that both the
H2 evolution and the reduction of PbSO4 processes in the negative
plates have been promoted obviously with the addition of the GO
samples [25]. From GO-1 to GO-3, their EH values become slightly more
positive while IEH increases to some extent, but IH,-1.4V increase largely.
Compared with GO-1, GO-4 has more positive EH and larger IEH and
IH,-1.4V values. Among the studied negative plates, the GO-4 plate con-
Fig. 3. Cathodic polarization curves of the negative plates (Blank, GO-1, GO-2, taining GO4-H has relatively larger IEH and smaller IH, −1.4V values,
GO-3, and GO-4) in H2SO4 solution (1.28 g cm−3). suggesting that GO4-H may be a more appropriate additive for the
negative plate. Apparently, the promotion effect of the four GO samples
on the hydrogen evolution and the reduction of PbSO4 is different.
Table 3
Characteristic parameters obtained from the results in Fig. 3 and the parallel Because the GO samples have different oxygenated groups (see
experiments. Table 2), the above results imply that different oxygenated groups may
play a different role in these promotion effect, which is discussed later.
Samples EH (V, vs. Hg/Hg2SO4) IEH (mA cm−2) IH,-1.4V (mA cm−2)

Blank −1.298 ± 0.005 0.67 ± 0.16 0.31 ± 0.21

GO-1 −1.269 ± 0.001 1.74 ± 0.29 1.79 ± 0.08 3.3. HRPSoC cycle life of the simulated test cells
GO-2 −1.249 ± 0.002 1.85 ± 0.29 3.57 ± 0.51
GO-3 −1.244 ± 0.005 2.27 ± 0.30 6.10 ± 0.72 The Vdischarge - cycle number curves of the simulated test cells with
GO-4 −1.253 ± 0.005 1.99 ± 0.21 2.77 ± 0.15
the negative plates containing different GO samples are shown in Fig. 4,
which were measured under the HRPSoC condition within 2C-3set.
According to the results in Fig. 4 and the parallel tests (at least three
times), the average HRPSoC cycle life (CL) of the test cells and its
standard deviation are obtained, as shown in Table 4 [24,25]. From
Fig. 4 and Table 4, it can be seen that the addition of the GO samples in
the negative plates can significantly increase the CL of the simulated
test cells and those containing GO4-H have the longest CL value. These
results are consistent with our previous work [24] and suggest that
GO4-H may be a more appropriate additive for the negative plate.

3.4. Microstructure of the negative plates

Fig. 5 shows the SEM morphologies of the NAM in the negative

Fig. 4. Vdischarge - cycle number curves under the HRPSoC condition for the
simulated test cells with different negative plates (Blank, GO-1, GO-2, GO-3,
and GO-4) at the 2C discharge rate within the third cycle-set.
3.2. H2 evolution performance of the negative plate
Fig. 3 shows the cathodic polarization curves of the negative plates
(Blank, GO-1, GO-2, GO-3, and GO-4) in H2SO4 solution (1.28 g cm−3),
which display the same features that have been discussed in our pre-
vious paper [24,25]. In this case, the same characteristic parameters
plates (Blank, GO-1, GO-2, GO-3 and GO-4) freshly prepared and tested
after 2C-3set. For the freshly prepared negative plates, those containing
various GO samples display more porous surface than the blank plate,
especially the GO-4 plate has large irregular holes and lamellar struc-
ture, as shown in Fig. 5(AI–EI). The BET surface area (SBET) and total
pore volume (Vpore) of these freshly prepared negative plates are pre-
sented in Fig. 6. Before the cycle test, the negative plates containing
various GO samples have much larger SBET and Vpore than those of the
blank plate, which demonstrate their change in microstructure with the
addition of GO additives. After the 2C-3set cycle test, the PbSO4 crystal
size on the surface of GO-1, GO-2, GO-3 and GO-4 plates becomes much
smaller than that on the blank plate, as shown in Fig. 5(AII–EII), im-
plying that the GO additives prevent the growth of PbSO4 crystals on
the negative plates.

Table 4
HRPSoC cycle life of the test cells within the 2C-3set cycle test.
Discharge rate Blank GO-1 GO-2 GO-3 GO-4

2C 374 ± 110 13527 ± 1402 15954 ± 1877 11580 ± 4340 19672 ± 1387

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Fig. 5. SEM images of the NAM in the negative plates before (I) and after the HRPSoC cycle test (II): (A) Blank; (B) GO-1; (C) GO-2; (D) GO-3, (E) GO-4. (The negative
plates were fully recharged after the 2C-3set test).

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Fig. 6. Specific surface and pore analysis results for the negative plates (Blank,
GO-1, GO-2, GO-3, and GO-4) before the HRPSoC cycle test.
Fig. 7. Water contact angles for the NAM in the negative plates (Blank, GO-1,
GO-2, GO-3, and GO-4).
4. Discussion
4.1. Effect of different GO oxygenated groups on the H2 evolution process
The H2 evolution can take place on the surface of Pb particles (SPb)
Fig. 8. Real negative plate (a) and schematic diagrams for (b) GO1-M, GO3-M and GO4-H; and for the cross section of (c) the Blank, (d) GO-1 and (e) GO-4 plates.
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Journal of Energy Storage 18 (2018) 414–420
and GO (SGO) in the negative plates [36,37] and therefore, their surface
features and real reaction area (Sreal = SPb + SGO) determine its re-
action rate [24,25]. The SBET and Vpore of the negative plates containing
the GO samples increase obviously than those of the blank plate (see
Fig. 6), which can largely increase their Sreal [25]. In this case, the H2
evolution in these negative plates is accelerated (see Table 3) [24,25].
For the plates of GO-1, GO-2, and GO-3, there is no obvious dif-
ference among their SBET and Vpore values (see Fig. 6), suggesting that
their Sreal should be approximated with each other, but their IH, −1.4V
values increase obviously from GO-1 to GO-3 (see Table 3). Thus, it can
be speculated that the promotion of the H2 evolution process in these
plates should be mainly ascribed to the GO surface features, i.e., the
different oxygenated groups on GO. Because only the content of CeO
groups (CeOH and CeOeC) increases obviously from GO1-M to GO3-M
(see Table 2), it can be deduced that an increase in the CeO groups on
the GO samples can promote the H2 evolution.
The GO-4 plate has the largest SBET and Vpore among the four plates
containing the GO additives, but its IH, −1.4V increase slightly than that
of the GO-1 plate (see Table 3), which may be related to the relatively
higher contents of C]O and OeC]O groups on GO4-H. Even though
the C]O and OeC]O groups on GO can promote H2 evolution, they
are also the active sites for the electrodeposition of Pb [8] to decrease
SGO and weaken their promotion effect to some extent. In this case, the
GO-4 plate does not show the strongest H2 evolution performance.
According to the above discussion, all the oxygenated groups on GO
can promote the H2 evolution in the negative plate, especially the C–O
groups. In this case, other groups, such as reported pyrrole nitrogen
[38], or metal or metal oxide with higher EH [6,7,39] need to be
modified on GO to inhibit the H2 evolution, which will be performed in
our future research.
4.2. Effect of different GO oxygenated groups on the HRPSoC cycle life of
the simulated test cells
Generally, the CL of the simulated test cells is controlled by the
growth rate of PbSO4 crystals in the negative plates [1,24,25]. Ac-
cording to Pavlov et al. [36], under the HRPSoC condition of this work,
the dominating elementary processes in the negative plates should be
the electrochemical reactions of Pb oxidation and PbSO4 reduction, and
the chemical reactions of formation and dissolution of PbSO4. In this
case, the effect of the capacitive charging and discharging processes on
the growth of PbSO4 crystals in the negative plates should not be the
main issue. With an increase in the SBET and Vpore of the GO-1, GO-2,
GO-3 and GO-4 plates (see Fig. 6), their largely increased Sreal provides
W. Cai et al.
extra nucleation sites for PbSO4 crystals to facilitate the formation of
the small-sized PbSO4 crystals with higher solubility [24,25,40]. Thus,
the reduction of PbSO4 crystals is accelerated for the increase in the
dissolution of PbSO4 crystals. The obvious increase in IEH of these plates
(see Fig.3 and Table 3) can prove this acceleration effect [24,25].
Moreover, smaller PbSO4 crystals on the surface of these negative
plates, as shown in Fig. 5(AII–EII), further verify that the addition of the
GO additives suppresses the growth of PbSO4 crystals. As a result, the
CL of the simulated test cells is significantly prolong (see Fig. 4 and
Table 4). This effect of the GO additives should be ascribed to their
change on the microstructure of the negative plates [4].
Another effect of GO may result from its obvious water absorb-
ability, which can influence its dispersion state in the NAM to change
the microstructure of the negative plate, meanwhile, increase the hy-
drophilicity of the NAM to facilitate acid diffusion into their inner vo-
lume at high rates of charge and discharge [34,41]. Therefore, the Sreal
of the negative plate can be further enlarged to impede the growth of
PbSO4 crystals. In order to confirm the above speculation, water contact
angle tests were performed for the NAM in the Blank, GO-1, GO-2, GO-3
and GO-4 plates to verify their difference [42]. The prepared negative
plate was dried in vacuum and ground into powder, and then the
powder was pressed to a smooth sheet under a pressure of 1960 N cm−2
for the contact angle test, as shown in Fig. 7. The NAM in the blank
plate shows hydrophobicity, while those containing the GO samples
show hydrophilicity, which seems to increase with the oxidation degree
of the GO samples (except GO4-H, see Table 2). The increase in the
hydrophilicity of the NAM containing GO4-H may be related to its re-
latively higher contents of C]O and OeC]O groups. The GO samples
in the NAM indeed increase its water absorbability.
Fig. 8 presents the schematics to show the comprehensive effects of
different GO samples on the negative plates. The GO-1 and GO-4 plates
are selected for the comparison because GO1-M and GO4-H have si-
milar oxidation degree but different contents of oxygenated groups (see
Table 2). The NAM in GO-4 has moderate hydrophilicity to facilitate
acid diffusion into the inner of the plate, while the GO-4 plate has the
largest SBET and Vpore (see Fig. 6). These two effects may result in the
largest Sreal to prevent the growth of PbSO4 crystals (as shown in
Fig. 8c– e). Therefore, the simulated test cells containing GO-4 have the
longest CL (see Table 4). These results suggest that higher hydro-
philicity of GO (such as GO3-M, see Fig.7) may be harmful to its dis-
persion in NAM resulting in a decrease in the SBET and Vpore of the
negative plate (such as GO-3, see Fig. 6). Contrarily, the lower hydro-
philicity of GO (such as GO1-M, see Fig.7) may weaken the acid dif-
fusion into the inner of the plate so as to reduce the inhibition effect on
the growth of PbSO4 crystals (as shown in Fig. 8d) and therefore, de-
crease the CL of the test cells (see Table 4). The hydrophilicity of GO is
closely related to its oxidation degree, which is mainly determined by
the contents of CeO groups. In this case, the GO samples with relatively
lower CeO groups and higher contents of C]O and OeC = O groups
(e.g. GO4-H) to maintain a moderate hydrophilicity may be more ap-
propriate as the additives of the negative plates.
5. Conclusions
(1) The addition of the GO samples (GO1-M, GO2-M, GO3-M, GO4-H)
with different oxygenated groups can largely promote the H2 evo-
lution and reduction of PbSO4 processes in the negative plate. An
increase in the content of CeO (CeOH and CeOeC) groups of GO
has strong promotion effect on the H2 evolution process.
(2) The addition of the GO samples can increase the HRPSoC cycle life
of the simulated test cells significantly and those containing GO4-H
have the longest cycle life.
(3) The addition of the GO samples can largely increase the SBET and
Vpore of the negative plate. In addition, the GO samples obviously
increase the hydrophilicity of the NAM. The negative plate
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Journal of Energy Storage 18 (2018) 414–420
containing GO4-H has moderate hydrophilicity, the largest SBET and
Vpore.
(4) GO with relatively lower contents of CeO groups and higher con-
tents of carbonyl and carboxyl groups (e.g. GO4-H) seems to be
more appropriate as the additive of negative plates.
Acknowledgments
The authors appreciate the analysis support of State Key Laboratory
of Material Processing and Die & Mould Technology and Center of
Forecasting and Analysis, Huazhong University of Science and
Technology.
References
[1] L.T. Lam, N.P. Haigh, C.G. Phyland, A.J. Urban, J. Power Sources 133 (2004)
126–134.
[2] P.T. Moseley, D.A.J. Rand, B. Monahov, J. Power Sources 219 (2012) 75–79.
[3] E. Ebner, D. Burow, A. Börger, M. Wark, P. Atanassova, J. Valenciano, J. Power
Sources 239 (2013) 483–489.
[4] D. Pavlov, P. Nikolov, T. Rogachev, J. Power Sources 196 (2011) 5155–5167.
[5] D.G. Enos, S.R. Ferreira, H.M. Barkholtz, W. Baca, S. Fenstermacher, J.
Electrochem. Soc. 164 (2017) A3276–A3284.
[6] B. Hong, L. Jiang, H. Xue, F. Liu, M. Jia, J. Li, Y. Liu, J. Power Sources 270 (2014)
332–341.
[7] L. Zhao, B. Chen, J. Wu, D. Wang, J. Power Sources 248 (2014) 1–5.
[8] L. Wang, H. Zhang, G. Cao, W. Zhang, H. Zhao, Y. Yang, Electrochim. Acta 186
(2015) 654–663.
[9] J. Xiang, C. Hu, L. Chen, D. Zhang, P. Ding, D. Chen, H. Liu, J. Chen, X. Wu, X. Lai,
J. Power Sources 328 (2016) 8–14.
[10] J. Lian, W. Li, F. Wang, J. Yan, K. Wang, S. Cheng, K. Jiang, J. Electrochem. Soc.
164 (2017) A1726–A1730.
[11] P. Bača, K. Micka, P. Křivík, K. Tonar, P. Tošer, J. Power Sources 196 (2011)
3988–3992.
[12] M. Fernández, J. Valenciano, F. Trinidad, N. Muñoz, J. Power Sources 195 (2010)
4458–4469.
[13] N. Sugumaran, P. Everill, S.W. Swogger, D.P. Dubey, J. Power Sources 279 (2015)
281–293.
[14] M. Saravanan, P. Sennu, M. Ganesan, S. Ambalavanan, J. Electrochem. Soc. 160
(2012) A70–A76.
[15] R. Marom, B. Ziv, A. Banerjee, B. Cahana, S. Luski, D. Aurbach, J. Power Sources
296 (2015) 78–85.
[16] A. Banerjee, B. Ziv, E. Levi, Y. Shilina, S. Luski, D. Aurbach, J. Electrochem. Soc.
163 (2016) A1518–A1526.
[17] S.M. Kumar, S. Ambalavanan, S. Mayavan, RSC Adv. 4 (2014) 36517–36521.
[18] K.Y. Kan, X. Zhang, S.C.T. Kwok, F. Ciucci, M.M.F. Yuen, RSC Adv. 5 (2015)
71314–71321.
[19] Q. Long, G. Ma, Q. Xu, C. Ma, J. Nan, A. Li, H. Chen, J. Power Sources 343 (2017)
188–196.
[20] P.T. Moseley, J. Power Sources 191 (2009) 134–138.
[21] M. Blecua, E. Fatas, P. Ocon, B. Gonzalo, C. Merino, F. de la Fuente, J. Valenciano,
F. Trinidad, Electrochim. Acta 257 (2017) 109–117.
[22] D. Pavlov, P. Nikolov, J. Electrochem. Soc. 159 (2012) A1215–A1225.
[23] P. Tong, R. Zhao, R. Zhang, F. Yi, G. Shi, A. Li, H. Chen, J. Power Sources 286
(2015) 91–102.
[24] H. Yang, Y. Qiu, X. Guo, Electrochim. Acta 235 (2017) 409–421.
[25] H. Yang, Y. Qiu, X. Guo, Electrochim. Acta 215 (2016) 346–356.
[26] J. Chen, B. Yao, C. Li, G. Shi, Carbon 64 (2013) 225–229.
[27] J. Chen, Y. Zhang, M. Zhang, B. Yao, Y. Li, L. Huang, C. Li, G. Shi, Chem. Sci. 7
(2016) 1874–1881.
[28] C.K. Chua, M. Pumera, Chem. Soc. Rev. 43 (2014) 291–312.
[29] Y. Tang, Y. Liu, W. Guo, T. Chen, H. Wang, S. Yu, F. Gao, J. Phys. Chem. C 118
(2014) 24866–24876.
[30] J. Chen, F. Chi, L. Huang, M. Zhang, B. Yao, Y. Li, C. Li, G. Shi, Carbon 110 (2016)
34–40.
[31] H. Wang, X. Yuan, Y. Wu, H. Huang, G. Zeng, Y. Liu, X. Wang, N. Lin, Y. Qi, Appl.
Surf. Sci. 279 (2013) 432–440.
[32] S. Stankovich, R.D. Piner, S.T. Nguyen, R.S. Ruoff, Carbon 44 (2006) 3342–3347.
[33] T. Szabó, O. Berkesi, I. Dékány, Carbon 43 (2005) 3186–3189.
[34] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu,
S.T. Nguyen, R.S. Ruoff, Carbon 45 (2007) 1558–1565.
[35] J. Zhang, H. Yang, G. Shen, P. Cheng, J. Zhang, S. Guo, Chem. Commun. 46 (2010)
1112–1114.
[36] D. Pavlov, P. Nikolov, J. Power Sources 242 (2013) 380–399.
[37] W.L. Zhang, J. Yin, Z.Q. Lin, J. Shi, C. Wang, D.B. Liu, Y. Wang, J.P. Bao, H.B. Lin, J.
Power Sources 342 (2017) 183–191.
[38] H.M. Jeong, J.W. Lee, W.H. Shin, Y.J. Choi, H.J. Shin, J.K. Kang, J.W. Choi, Nano
Lett. 11 (2011) 2472–2477.
[39] L. Zhao, B. Chen, D. Wang, J. Power Sources 231 (2013) 34–38.
[40] D. Pavlov, P. Nikolov, T. Rogachev, J. Power Sources 195 (2010) 4435–4443.
[41] J. Xiang, P. Ding, H. Zhang, X. Wu, J. Chen, Y. Yang, J. Power Sources 241 (2013)
150–158.
[42] A. Yan, X. Xiao, I. Külaots, B.W. Sheldon, R.H. Hurt, Carbon 44 (2006) 3116–3120.