Journal of Energy Storage 41 (2021) 102785

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Journal of Energy Storage

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Using silkworm excrement and spent lead paste to prepare additives for
improving the cycle life of lead-acid batteries
Yi Tao Hu a, b, Jie Cai Li a, b, Asad Ali a, Pei Kang Shen a, *
a
Collaborative Innovation Center of Sustainable Energy Materials, Guangxi Key Laboratory of Electrochemical Energy Materials, Guangxi University, Nanning 530004,
China.
b
School of Physical Science and Technology, Guangxi University, Nanning 530004, China.

A R T I C L E I N F O A B S T R A C T

Keywords: Sulfation at the negative electrode remains a crucial failure in lead-acid batteries. To overcome the sulfation
Biomass Carbon issue, herein, a silkworm excrement-based porous carbon (SEPC) material has been successfully synthesized by a
Spent lead-acid battery recovery facile one-step metal catalytic cracking method. Consequently, SEPC and desulfurization spent lead paste were
Cycle life
mixed and calcined to obtain a composite material of SEPC and PbO (SEPC-PbO), and employed as the negative
Depth of Discharge (DOD)
additive to suppress the sulfation of lead-acid battery. The morphological characterization exhibits that SEPC has
a plentifully mesoporous structure. The specific discharge capacity of the SEPC-PbO negative plate is 165 mAh
g− 1 (11.5% higher than the negative plate of traditional lead-acid battery) and ensuring remarkable suppression
of hydrogen evolution. After 400 100% depth of discharge (DOD) cycles, the capacity retention rate is still as
high as 84% and after 3000 5%DOD cycles, the active substances of the SEPC cell remained high reversible. In
addition, the development of new lead-acid batteries, the synthesis of biochar materials, and the combination of
waste lead paste recycling industries were explored. All these contribute to the decrease of the pollution risk of
the silkworm breeding and lead-acid battery recovery industry and revolutionize the sustainable utilization of
carbon resources.

1. Introduction
With the promising development of the transportation, automobiles,
and telecommunication industries, lead-acid batteries have been widely
used as their power sources. [1] The lead-acid battery has the advan­
tages of low cost, simple production process, mature recovery technol­
ogy, and stable performance. [2–4] As is well known, researchers are
interested in the application of lead-acid batteries in hybrid electric
vehicles. Although the lead-acid battery is widely used, its service life is
short, which brings frequently spent lead paste that needs to be recycled.
[5] Fortunately, the considerable residual value of spent lead-acid bat­
teries has established the recycling industry of lead-acid batteries. [6,7]
In recent years, the recycling methods and technologies of waste lead
paste have been significantly developed. [8–10] Researchers trying to
recover beneficial things from the waste lead paste by reduce energy
consumption and improve the recovery rate as much as possible. For
instance, Liu et al. proposed a green and efficient process to recover high
purity α-PbO from the waste residue of lead-acid batteries. [8]
Furthermore, Lin et al. attempted to recover high-purity lead
tetrahydrate products from the waste lead-acid battery paste using a
closed-loop ammonium salt system. [11] Xie et al. attempted to recover
lead from the waste lead paste by pre-desulfurization and
low-temperature reduction smelting. [12] Previously, some valuable
electrode materials are recovered from the waste lead-acid batteries and
realized the sustainable utilization of resources to a certain extent.
However, there are still some shortcomings, such as high energy con­
sumption, single recycled electrode materials, and easy cause secondary
pollution in the preparation process.
At the same time, some discarded biomass materials have been used
as raw materials for the preparation of high-performance carbon mate­
rials. [13] These biomass carbon materials deliver many applications
and practices in the fields of sewage treatment, electrochemical energy
storage, and electrochemical catalysis. [14–16] Porous carbon nano­
sheets prepared with oak nutshells can be used in supercapacitors. [17]
These works have realized the recovery and utilization of many kinds of
solid wastes, including waste biological materials, but there are many
impurities in the recovered waste materials, unstable sources, and
cumbersome recovery process. More importantly, the silkworm an

* Corresponding author.
E-mail address: pkshen@gxu.edu.cn (P.K. Shen).

https://doi.org/10.1016/j.est.2021.102785
Received 8 December 2020; Received in revised form 30 April 2021; Accepted 29 May 2021
Available online 25 June 2021
2352-152X/© 2021 Published by Elsevier Ltd.
Y.T. Hu et al.
ancient economic insect is the main source of raw materials for silk.
Silkworms are widely cultivated in the Yangtze River Delta and Pearl
River Delta regions in China. Silkworms have been brought good eco­
nomic benefits but silkworm breeding inevitably brings the problem of
silkworm excrement disposal. Silk derivatives have been used in bio­
pharmaceuticals and cosmetics, while silkworm excrement has been
regarded as a vital raw material of Chinese herbal medicines. Silkworm
excrement-based carbon has been used in supercapacitors, but it is
rarely used in other fields of electrochemistry. [18] The preparation of
high-performance lead-acid batteries by adding carbon materials into
the negative active materials (NAM) of traditional lead-acid batteries
has become a major trend in the development of the lead-acid batteries
industry. [19,20] Lead-carbon battery has inherited many advantages of
lead-acid battery, and its service life has been considerably improved. It
has great application potential in the field of electrochemical energy
storage. [21–23] However, lead-carbon batteries still need to find effi­
cient carbon material additives, a new paste process, and the solving of
hydrogen evolution and water loss problems. [24,25]
Herein, we synthesized silkworm excrement-based porous carbon
(SEPC) from silkworm excrement by one-step metal catalysis. Then
SEPC and desulfurized spent lead paste were mixed and calcined to
prepare the SEPC-PbO. Finally, it was employed as an additive of NAM
in the lead-acid battery. Furthermore, the PbO adhesion on the SEPC
surface can make SEPC and NAM mix evenly, and inhibit SEPC hydrogen
evolution, and develop the battery to have better long-cycle perfor­
mance. In addition, the addition of SEPC-PbO also improved the con­
ductivity of the negative active material and provided a stable channel
for the flow of electrolytes. Previous work in the field of lead-acid bat­
tery mainly focused on improving the specific capacity of electrode
materials and the cycle performance of high rate part state of charge
(HRPSoC) (Table S1, support information), but the low rate deep charge-
discharge performance of the battery is often ignored (because the test
takes a long time). But in the actual application process, such as power
battery, users often do deep discharge to the battery because they don’t
understand the characteristics of lead-acid battery or the need of high-
intensity work. Secondly, when the lead-acid battery is used as the en­
ergy storage battery of a renewable energy power station, it will have to
discharge the battery deeply in the peak period of power consumption.
Deep discharge often reduces the life of the lead-acid battery, but it is
Fig. 1. Schematic of preparation of the SEPC-PbO.
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Journal of Energy Storage 41 (2021) 102785
inevitable in practical application, so it is of practical significance to
study the life of a lead-acid battery under the condition of low rate deep
charge-discharge. Therefore, the battery life test in this paper mainly
focuses on the cycle performance of the battery under 100% DOD con­
dition for a long time.
2. Experimental and methods
2.1. Synthesis of SEPC-PbO
The novel lead-carbon composite was synthesized as follows in
Fig. 1. Initially, 20 g of high-quality silkworm excrement is placed at
60◦ C in a vacuum drying oven for 48 h and then ground into silkworm
excrement powder. Then 10 g silkworm excrement powder was added
into 200 mL Ni (NO3)2•6H2O solution (0.1 mol L− 1), stirred for 10 h,
washed with deionized water, filtered, and dried. After that, the as-
obtained silkworm excrement powder was added into 500 mL KOH
(50 g) ethanol solution, magnetically stirred to paste, kept at room
temperature for 10 h, dried in vacuum at 70 ◦ C, and grind it using mortar
and pestle. The comminuted products were placed in a tubular furnace,
protected by nitrogen, and raised from room temperature to 850 ◦ C at a
heating rate of 2 ◦ C min− 1, and kept for 2 h. Consequently, the product
was treated with 3 mol L− 1 HCl and then washed with deionized water
until the filtrate was neutral. The product was filtered and dried for 24 h
at 70 ◦ C. The preparation process of SEPC-PbO represent as follows: (i)
Using (NH4)2CO3 to pre desulphurize spent lead paste. (ii) Pb(NO3)2 was
produced by adding the desulfurized waste lead paste into dilute HNO3
containing H2O2. (iii) Pb(NO3)2 was precipitated into PbCO3 by Na2CO3.
(vi) Mixing 5 g SEPC and 0.5 g desulfurized spent lead paste (PbCO3)
evenly, they were placed in a tube furnace protected by nitrogen and
calcined at 450 ◦ C for 2 h to prepare SEPC-PbO.
2.2. Physical characterization
X-ray diffraction (XRD) analysis was performed on a D/Max-III X-ray
diffractometer (Rigaku Co., Japan) with Cu Kα radiation, a voltage of 40
kV, and a current of 30 mA. The specific surface area and pores size
distribution of the samples were studied using an ASAP 2460 Surface
Area Analyzer (Micromeritics Co., USA). Field emission scanning
Y.T. Hu et al.
electron microscopy (FESEM; SU8820, Hitachi Co., Japan) was applied
to characterize the morphology distribution of the samples. Raman
spectroscopy was carried out on a Raman spectrometer (Horiba Jobin
Yvon Inc., France) using a 532 nm He/Ne laser from 500 cm− 1 to 4000
cm− 1. X-ray photoelectron spectroscopy (XPS, SMARTLAB3KW) was
used to characterize the chemical composition and bonds.
2.3. Electrodes preparation and electrochemical measurements
To characterize the properties of carbon materials, cyclic voltam­
metry (CV) measurements were carried out on the IM6 electrochemical
workstation with a three-electrode system. CV tests were performed at a
scan rate of 5 mV s− 1 in the potential range 0 V to -1.2 V. The working
electrodes were prepared by mixing one of the carbon materials (80 wt
%), acetylene black (10 wt%), and poly(vinylidene fluoride) (PVDF) (10
wt%) in the N-methyl-2-pyrrolidone (NMP) solvent; thereafter, the
seriflux was coated onto a titanium sheet with a nominal area of 2*1cm2
and dried under vacuum at 60 ◦ C for 10 h. The reference electrode was a
Hg/Hg2SO4 (0.615 V vs. SHE), and the counter electrode is a graphite
rod. The electrolyte of the three-electrode system is 1.28 gmL− 1 H2SO4
solution. Under the same conditions, negative plates (12 mm*8 mm*1.5
mm) were used as working electrodes, and very large positive plates (70
mm*40 mm*1.5 mm) were used as pair electrodes to test the CV (voltage
range of -0.3 V to -1.5 V, sweep speed of 5 mV s− 1) and LSV (voltage
range of -1 V to -1.5 V, sweep speed of 1 mV s− 1) of the negative plate
(the fabrication method of the cell and negative plate is in the support
information). The electrochemical impedance spectroscopy (EIS) of the
cells was measured in the two-electrode system using the IM6 electro­
chemical workstation of Zahner-Elektrik Company in Germany. The EIS
was performed in the frequency range of 0.1 Hz - 30 kHz at an amplitude
of 5 mV and voltage of -1.3 V (after 30 min potentiostatic polarization at
the voltage of -1.3 V). The specific capacitance of carbon material could
be calculated from the CV curves according to the following equation.
Cm = SCV /2mυΔV
Where Cm represents the specific capacitance (F g− 1), SCV is the area of
Fig. 2. (a) and (b) are SEM images of SEPC, (c) SEM images of SEPC SEPC-PbO,(d) Pore-size distribution of SEPC and SEPC-PbO, (e) XRD pattern of SEPC-PbO.
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Journal of Energy Storage 41 (2021) 102785
CV curve, m is the mass of active materials in the working electrode (g),
υ is the scan rate of CV curve (V s− 1) and ΔV is the width of the potential
window (V). All the tests were performed at room temperature.
3. Results and discussion
3.1. Physical and chemical characterization of SPEC-PbO
The morphology and microstructure of the as-prepared materials
were analyzed by SEM measurements. It is observed from the SEM im­
ages of the spent lead paste that a large number of huge particles of lead
sulfate and a very small amount of active lead substance are present
(Fig. S1a, supporting information). The irreversible sulfurization of the
negative electrode is the root cause of the failure of the lead-acid battery.
The XRD test of spent lead paste also shows the main components are
lead sulfate and lead (Fig. S1b, Supporting Information). As shown in the
SEM of Fig. 2a, the SEPC has a pore network structure. In addition,
Fig. 2b shows that SEPC also has a lamellar structure like graphite
sheets. The generation of these porous networks is mainly due to the
pore making the effect of KOH in the preparation process of SEPC, while
the lamellar structure similar to graphite sheet is substantially benefited
from the catalysis of transition metal nickel in the synthesis process. [26,
27] The mesh porous structure will facilitate the storage and circulation
of the electrolyte. [28] In the SEM image of SEPC-PbO (Fig. 2c), a large
number of lead oxide particles were attached to the pore wall of SEPC.
The porous structure and specific surface area parameters of SEPC were
evaluated by N2 adsorption-desorption. (Fig. 2d) The surface area, pore
size, and pore volume results of SEPC are shown in Table 1. The SEPC
material has a specific surface area of 1306.5 m2 g− 1 and is rich in
Table 1
Porous structure parameters of SEPC and SEPC-PbO.
Samples SBET (m2 g− 1) Average pore size (nm) Pore volume (cm3 g− 1)
SEPC 1306.5 6.03 1.24
SPEC-PbO 990.5 5.05 0.55
Y.T. Hu et al.
microporous, mesoporous, and macroporous structures. More impor­
tantly, a larger specific surface area can provide a larger specific
capacitance for the SEPC, to buffer the damage of large current to the
NAM. However, the specific surface area, pore size, and pore volume of
SEPC-PbO composite decreased, because PbO particles adhered to the
SEPC hole. The graphitization and crystal morphology of SEPC-PbO has
been further confirmed by XRD analysis. The typical XRD spectrum of
SEPC-PbO shows in Fig. 2e that the lead in SEPC-PbO exists mainly in
the form of Pb and PbO. Notably, the PbO was typically α-PbO, because α
-PbO was more stable than β-PbO at 450 ◦ C. [29,30] In addition,
compared with the XRD pattern of SEPC before HCl solution treatment
(Fig. S2, supporting information), no nickel diffraction characteristic
peak was found in Fig. 2e, indicating that nickel element in SEPC has
been completely removed.
Additionally, the carbon constituent in SEPC was further character­
ized by the Raman spectroscopy (Fig. S3, supporting information). In
particular, the characteristics peak of 1351 cm− 1 and 1586 cm− 1 are
assigned to the D and G bands, respectively. The 2D peak at 2703 cm− 1
corresponds to the two iTO phonons at the K point and is sometimes
regarded as the G band. The D, G, and 2D bands are the intrinsic vi­
brations of the graphene sheets. [31] Generally, the ID/IG ratio can be
applied to estimate defect and disorder degree in carbon composites.
In order to analyze the chemical composition and valence states of
SEPC and SEPC-PbO materials, XPS analysis was performed. Fig. 3a
shows the XPS spectra of SEPC and SEPC-PbO powders. Peaks at 130-
155 eV, 280-300 eV, and 525-545 eV correspond to the binding en­
ergies of Pb4f, C1s, and O1s, respectively. The XPS spectrum of C1s can
be decomposed into four peaks (Fig. 3b), and the characteristic peaks
observed at approximately 284.6 eV are from the graphitized C-C bond.
In addition, the band energies located at 286.4 eV, 289.0 eV, and 291.0
eV are generally classified as C-O functional groups, O=C-O functional
groups, and OCOO functional groups, respectively. The presence of PbO
and Pb-COO bonds in the SEPC-PbO composite indicates that the
Fig. 3. (a) XPS spectra of SEPC and SEPC-PbO powders, (b) C1s XPS spectra of SEPC-PbO, (c) Pb4f XPS spectra of SEPC-PbO, (d) O1s XPS spectra of SEPC-PbO.
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Journal of Energy Storage 41 (2021) 102785
composite formed by calcining carbon with lead is more stable than
simple lead-carbon mixtures because of the strong forces between the
carbon and lead (Fig. 3c). [29] Moreover, as shown in Fig. 3d, the XPS
map of O 1s can be decomposed into four parts, Pb-O (530.97 eV), -OH
(531.78 eV), C-O (532.68 eV), and C=O (533.56 eV). Generally, C=O
refers to acidic functional groups on the surface of carbon materials,
indicating that SEPC-PbO has certain hydrophilicity. [32].
We found that the CV curves of all three materials are close to the
rectangle, indicating that all three materials possess good capacitive
properties (Fig. S4a, Supporting Information). The specific capacitors of
CCB, SEPC, and SEPC-PbO were 53.18 F g− 1, 102.43 F g− 1, and 113.65 F
g− 1, respectively. [33] It is worth noting there is a weak reduction peak
(− 1.05 to − 1.15 V) in the SEPC-PbO curve, indicating that Pb2+ is
reduced to Pb. The oxidation peak between − 1.1 to − 1.0 V indicates that
Pb is oxidized to form PbSO4. [34] The existence of a redox peak in­
dicates PbO provides pseudo-capacitance for SEPC-PbO. Therefore,
SEPC-PbO is slightly more capacitive than SEPC. The electrochemical
stability of SPEC-PbO was tested (Fig. S4b, Supporting Information). The
CV curve of SEPC changed little before and after the test, indicating that
the electrochemical performance of SEPC remained stable. However, we
also found that the oxidation peak strength of Pb decreased, indicating
that part of lead sulfate is irreversible in the cycling process. [35] The
SEM characterization and EDS analysis of SEPC-PbO showed a large
number of ultrafine lead sulfate particles were indeed generated on the
surface of SEPC (Fig. S5, Supporting information).
In addition, we also carried out a CV test on the experimental
negative plate to study the influence of different carbon materials on
electrode polarization. As shown in Fig. 4a, after the addition of carbon
material, the oxidation peak of the electrode moves in a positive direc­
tion, while the reduction peak moves in a negative direction. This is
mainly due to the polarization of the electrode material, indicating the
SEPC-PbO material provides good conductivity for the negative plate.
[19] The reversibility of the experimental negative plate is represented
Y.T. Hu et al.
Fig. 4. (a) CV curves of various negative plates, (b) LSV curves of various negative plates.
by the values of |IO|/|IR|. As shown in Table S2, the reversibility of
Pb/PbSO4 redox couple of experimental negative plate was compared
with the absolute ratio of reduction and oxidation peak current (|IR|/|
IO|). The |IR|/|IO| values of control, CCB, SEPC and SEPC-PbO negative
plate were 0.60, 0.67, 0.73 and 0.75, respectively. The highest |IR|/|IO|
ratio of the SEPC-PbO negative plate corresponds to the best revers­
ibility of Pb/PbSO4 redox of all experimental negative plates.
Considering the practical application, the LSV test is carried out for
the negative plate with the three-carbon materials are added. By
comparing and analyzing the hydrogen evolution current density of
different negative plates at -1.5V, the hydrogen evolution phenomenon
of them was studied. As shown in Fig. 4b, CCB with 0.05wt%− 0.1wt%
was only added to the negative electrode of traditional commercial lead-
acid battery(the hydrogen evolution current density is only 0.086 Ag− 1),
so the electrode would not face the hydrogen evolution problem. [36]
However, when the amount of CCB was increased to 1wt%, the
Fig. 5. (a) SEM image of the NAM after curing, (b) SEM image of NAM after formation, (c) SEM image of NAM after 5 hours discharge, (d) SEM image of NAM
after discharge.
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Journal of Energy Storage 41 (2021) 102785
hydrogen evolution current density of the CCB negative plate increased
(as high as 0.473 Ag – 1), and the phenomenon of hydrogen evolution
occurred at the electrode (the hydrogen evolution current density is
0.297 Ag− 1). The reason for SEPC negative plate hydrogen evolution is
probably that in the process of washing with HCl solution, the surface of
SEPC is oxidized and carries a large number of active groups, which
enhances SEPC’s hydrogen evolution ability. [37,38] Compared with
the SEPC negative plate, the hydrogen evolution current density of the
SEPC-PbO negative plate was slightly reduced (only 0.204 Ag− 1), indi­
cating that the hydrogen evolution of the SEPC-PbO negative plate was
inhibited to a certain extent. This may be due to the conversion of PbO
adsorbed in the SEPC pore wall into PbSO4 during the charge-discharge
reaction of SEPC-PbO. Studies have shown that PbSO4 can inhibit the
hydrogen evolution of lead-acid batteries. [35]
Y.T. Hu et al.
3.2. Effect of SEPC-PbO on cells
The influence of SEPC-PbO on the morphology of NAM at various
stages was investigated shown in Fig. 5. In the curing process, the free
lead in the lead powder is slowly oxidized to lead oxide. We can see in
Fig. 5a that a large amount of needle-like lead oxide is attached to the
surface of SEPC. This is because the SEPC is no longer simply in direct
contact with the lead powder during the paste process, but the lead
powder is in contact with the PbO attached to the SEPC surface. In the
SEM diagram after the formation of the negative plate (Fig. 5b), we can
see that the lead oxide, which was initially in the shape of a needle, has
been transformed into the spongy active material lead. As shown in the
SEM image (Fig. 5c) the NAM when the negative plate was discharged at
a rate of 0.1c for 5 h. It shows that part of the active substance lead
attached to the SEPC hole and surface has been transformed into lead
sulfate particles. The lead sulfate particles are embedded in the SEPC’s
pores, and their size is limited by the SEPC’s pores. We also observed the
absence of active materials in some of the holes, but this does not mean
the holes are idle, on the contrary, they are likely to contain a large
amount of electrolyte. [19] The SEM images of the NAM at the end of
discharge are shown in Fig. 5d. In the figure, the size of lead sulfate
particles varies greatly, but this indirectly indicates that SEPC restricts
the growth of some lead sulfate particles especially those coated in the
pore structure. Moreover, the addition of the SEPC-PbO can develop the
second phase among the discharged lead sulfate crystal particles and
restrain the crystal particle growth to allow retention of ion transport
channels. [35] The results of several performance tests on the experi­
mental cells are shown in Fig. 6. The initial discharge specific capacity
curve of the cells is shown in Fig. 6a. The SEPC-PbO cell exhibits the
highest specific discharge capacity (165 mAh g− 1 was higher than the
control cell 130 mAh g− 1, CCB cell 148 mAh g− 1, and SEPC cell 158 mAh
g− 1). In the early stage of lead-acid battery formation, the main com­
ponents of the electrode plate consist of a mixture of lead oxide and lead
sulfate, which has very low conductivity. The addition of carbon ma­
terials can improve the conductivity of the electrode plate. [19]
Therefore, the high specific capacity of the SEPC-PbO cell is mainly due
to SEPC’s conductivity and effective contact between SEPC and NAM.
[39] The content of metallic lead in the negative plate after formation
was analyzed by a chemical method is shown in Table 2 (the chemical
analysis method is in the support information).
After the cells were formed, to further study the influence of carbon
Fig. 6. (a) Initial discharge specific capacity of the test cells. (b) The Nyquist plots for test cells after formation. (c) Different discharge rates of the test cells, (d) 400
100%DOD cycles of test cells. (e) The Nyquist plots for test cells (after 400 100%DOD cycles). (f)) 3000 5%DOD cycles of test cells.
6
Journal of Energy Storage 41 (2021) 102785
Table 2
The content of Pb and PbSO4 in the negative plate of the cell after formation.
Component (wt.%) Control CCB SEPC SPEC-PbO
Pb 89.25 93.41 94.33 96.26
PbSO4 8.45 4.19 3.57 1.34
materials on the internal resistance of the cell, the electrochemical
impedance test (EIS) was carried out. The high-frequency region of the
Nyquist diagram is the charge transfer process, and the low-frequency
region is the material transfer process. [28] In Fig. 6b, the intersection
of the curve and the real axis in the high-frequency region is the solution
resistance (Rs) of the cell. The experiment cell used the same concen­
tration of electrolyte, but the Rs is different because, in the process of
cell formation, the addition of carbon materials of the cell hydrogen
evolution ability is stronger, more water is electrolyzed so that the
concentration of electrolyte becomes larger, Rs is reduced. The width of
the irregular arc in the high-frequency region represents the resistance
during the electrochemical reaction between the electrolyte and the
electrode surface (i.e., charge transfer resistance, Rct). The smaller the
width, the smaller the Rct. [40] In Fig. 6b, the semicircular arc in the
high-frequency region shrinks and disappears, indicating that the Rct of
the measured cells are all small and the charge transfer process is fast
(because the measured cells are all new cells) [25]. A straight line with a
slope of approximately 1 in the low-frequency region indicates that the
impedance of the cell is affected by ion diffusion in the electrolyte (i.e.
Warburg impedance, caused by concentration polarization within the
electrode). [25]
Fig. 6c shows the effect of SEPC-PbO content in the negative plate on
the cell capacity at various discharge rates. When the SEPC-PbO addi­
tion amount was 0.5wt%, the capacity of the cell was not significantly
increased at different discharge rates; when the SEPC-PbO addition
amount was 1wt%, the rate performance of the cell was significantly
improved. Under the condition of low rate discharge (0.1C, 0.2C, 0.5C),
the discharge capacity of the cell with SEPC-PbO content of 1.5wt% was
lower than that with SEPC-PbO content of 1wt%. However, the
discharge capacity of the cell with a SEPC-PbO content of 1.5wt% was
higher than that of the cell with a SEPC-PbO content of 1wt% under the
condition of high rate discharge (2C,3C). After the discharge test with a
3C rate, the cells were charged and discharged with a 0.1C rate. We
found the discharge capacity of the cell was still the highest when SEPC-
Y.T. Hu et al.
PbO content was 1wt%. Consequently, the SEPC-PbO content in the
negative plate will possess various effects on the discharge capacity of
the cell at different rates.
It is easy to form irreversible lead sulfate particles on the surface of a
lead-acid battery during the 100% depth of discharge (DOD) cycle [41].
Therefore, it is of great significance to study the reversibility of lead-acid
batteries and the improvement of the irreversible sulfate phenomenon
by carbon materials under the condition of 100%DOD. The experimental
cell was tested for 400 100%DOD cycles at a rate of 0.5c are shown in
Fig. 6d. The SEPC-PbO cells exhibit optimal reversibility with the
highest capacity retention rate after 400 100%DOD cycles (84%). We
found the cycle curve of the control cell is very different from the
lead-carbon cells. The capacity of the control cell always decays very
rapidly, while the capacity of the lead-carbon cell decays very slowly at
the beginning of the cycle.
We found that the capacity decay rates of CCB cell and SEPC cell
were accelerated after about 200 100%DOD cycles. The EIS of the
experimental cell is tested again, and the results are shown in Fig. 6e. In
Fig. 6e, the Rs of the control cell is the largest. This is because in the
repeated deep charge-discharge process, many sulfate ions have become
irreversible lead sulfate particles attached to the electrode surface and
can not return to the electrolyte, resulting in the decrease of electrolyte
concentration and the increase of Rs. The SEPC-PbO cell has the smallest
change in Rs, which indicates that the electrolyte concentration has little
change, so the SEPC-PbO cell system is also the most stable (this is also
confirmed by the results in Fig. 6d). In Fig. 6d, we also found that an
obvious arc appeared in the high-frequency region because irreversible
nonconductive lead sulfate particles were generated during the cycle
test of the cell, which attached to the electrode surface, which was not
conducive to the reaction between the electrolyte and the active mate­
rial lead, thus increasing the Rct of the cell. We can find that the Rct of
the cell with SEPC-PbO in the figure is the smallest, which indicates that
SEPC-PbO can promote the electrochemical reaction between the elec­
trolyte and active material lead, and can effectively reduce the Rct of the
cell. In the figure, the straight-line slope of the control cell in the low-
frequency region decreases(Warburg impedance is big), and it is in­
clined to the solid axis. [25] This is because the irreversible
non-conductive lead sulfate forms a dense film on the surface of the
electrode, which slows the diffusion rate of the electrolyte to the inside
of the electrode. The slope of the straight line of the SEPC-PbO cell is the
largest in the low-frequency region(Warburg impedance is small),
indicating that the porous structure of SEPC is conducive to the diffusion
of electrolyte inside the electrode. [25] The Rs, Rct, and Warburg
impedance of CCB and SPEC cells in the figure are both larger than that
of the SEPC-PbO cell, it shows that the increase of internal resistance is
the reason for the accelerated capacity attenuation. Therefore, by
comparison, SEPC-PbO can minimize the impedance of lead-acid bat­
teries under 100% DOD condition.
Combined with the results of the EIS and LSV test, it is speculated
that 100% DOD capacity attenuation of control cell is mainly caused by
irreversible sulfation of electrode materials. The rapid attenuation of
100%DOD capacity of CCB cell was mainly caused by the decrease of
CCB conductivity and loss of an electrolyte. The conductive mode of
carbon black is based on the "percolation theory", electrons move
through the conductive network formed by carbon black particles in the
system to realize conduction. However, with the increase of lead sulfate
particles, the efficiency of the method decreases, because the "conduc­
tive chain" formed by the carbon black particles will gradually be iso­
lated by the larger and larger lead sulfate particles, and the macroscopic
performance is the increase of the internal resistance of the cell (EIS
proves this). The capacity attenuation of the SEPC cell at 200 100%DOD
cycles is mainly due to the inability to inhibit hydrogen release from the
negative electrode. The 100%DOD capacity of the SEPC-PbO cell at­
tenuates slightly after about the 100th cycle, possibly because the PbO
attached to the SEPC is converted into an ultrafine PbSO4, which reduces
the SEPC conductivity. However, the production of PbSO4 reduces the
7
Journal of Energy Storage 41 (2021) 102785
hydrogen evolution of the negative plate and makes the 100%DOD cycle
performance of the cell more stable, which is undoubtedly worthwhile.
More importantly, in the discharge process, the lead sulfate formed by
lead will first nucleate on the lead sulfate particles on the surface of
SEPC, so that lead can avoid being coated by the generated lead sulfate
particles in a short time so that lead can continue to participate in the
discharge reaction. [42]
Some cars are equipped with a start-stop system, which requires the
battery to discharge in a short time with extraordinary power. For this
reason, 3000 5%DOD cycle tests were conducted on the cell at last (2C
discharge rate, test method in support information). The test results
show (Fig. 6f) that the SEPC-PbO cell has the most stable discharge
voltage during 3000 5%DOD cycles. After 3000 5%DOD cycles, the NAM
was characterized by SEM, and the proportion of lead sulfate and lead
was analyzed by chemical method (the analysis method is in the support
information). The SEM characterization results showed that the SEPC-
PbO cell NAM had the least lead sulfate particles, and the particle size
of lead sulfate particles was small (Fig. S6, Supporting Information). The
composition analysis results showed the metallic lead content in the
NAM of the SEPC-PbO cell was the highest (Table S3, support infor­
mation). The SEPC-PbO is helpful to improve the invertibility of Pb/
PbSO4 in the process of high current and short time discharge.
4. Conclusions
In summary, the additive has been successfully prepared using silk­
worm excrement and spent lead paste by metal catalytic cracking
method for the improvement of the cycling-life performance of lead-acid
batteries. The SEPC-PbO has a rich pore structure and stable electro­
chemical performance confirmed by characterization and experiments.
PbO is attached to the SEPC surface, which makes SEPC and NAM mix
more evenly, and indirectly improves the specific capacity of the nega­
tive plate (165 mAh g− 1). More significantly, the PbO on the SEPC
surface is converted into irreversible PbSO4 during charging and dis­
charging which inhibits hydrogen evolution. Therefore, the 100% DOD
cycle performance of the SEPC-PbO cell is the best (400 cycles, capacity
retention rate 84%). In this study, the development of a new high-
performance lead-acid battery, the treatment of silkworm excrement,
and the recovery of spent lead-acid paste was combined to alleviate the
pressure caused by environmental pollution and improve the utilization
rate of resources. More importantly, we are hopeful that our work
confers a new momentum in the sustainable development of the lead-
acid battery industry, silkworm breeding industry, and biochar mate­
rial industry.
Author Statement
For this paper, all the authors involved the writing, the discussion,
provided the comments and suggestions, also revised the manuscript.
Declaration of Competing Interest
We declare that all the authors contributed either on the experi­
mental or writing or discussion. There are no conflicts to declare.
Acknowledgments
This work was supported by the Guangxi Science and Technology
Project (AA17204083, AB16380030), the link project of the National
Natural Science Foundation of China and Fujian Province (U1705252).
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.est.2021.102785.
Y.T. Hu et al. Journal of Energy Storage 41 (2021) 102785

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