Journal of Membrane Science 572 (2019) 512–519

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Journal of Membrane Science

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

Sb2O3 modified PVDF-CTFE electrospun fibrous membrane as a safe lithium- T

ion battery separator
⁎
Lijuan Wang, Zhonghui Wang, Yi Sun, Xin Liang, Hongfa Xiang
School of Materials Science and Engineering, Anhui Provincial Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology, Hefei
230009, PR China

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

Keywords: A Sb2O3-modified poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) fibrous membrane is pre-

Electrospun nanofibers pared via a sequential electrospinning technique and used as a safe separator for lithium-ion batteries. A small
Separator amount of 2% Sb2O3 nanoparticles can effectively improve mechanical strength of the PVDF-CTFE membrane.
Safety Besides, the Sb2O3 modified PVDF-CTFE electrospun fibrous membrane exhibited synergistic flame retardancy as
Lithium-ion battery
well as outstanding thermal stability without shrinkage at 160 °C for 2 h. Furthermore, the Sb2O3-modified
PVDF-CTFE membrane as a composite separator possessed superior wettability toward nonaqueous electrolyte,
higher ionic conductivity, lower interfacial resistance and well electrochemical stability compared to the
commonly used polyethylene separator. Therefore, the Li||LiFePO4 cell using this type of composite separator
exhibits excellent cycling stability and superior rate capability. These results suggest that the Sb2O3-modified
PVDF-CTFE electrospun fibrous membrane is attractive for high-performance and high-safety lithium-ion bat-
teries.

1. Introduction Electrospinning has been widely used to prepare varieties of func-

In recent years, lithium-ion batteries (LIBs) play a key role in smart
electronic devices, electric vehicles (EVs) and grid energy storage sys-
tems with the advantages on energy density, power density and cycle
lifetime [1–4]. A thin micro-sized membrane is necessary as a separator
in the LIBs using liquid nonaqueous electrolytes. The separator keeps
the positive and negative electrodes apart in the battery, while allows
rapid transport of ionic charge carriers, especially the Li+ ion compa-
nied with the electrolyte [5–8]. Currently, conventional polyolefin se-
parators dominate the commercial LIBs market due to their relatively
high mechanical strength. However, polyolefin separators have some
drawbacks, including the low porosity of less than 50%, inferior wett-
ability toward liquid electrolytes, poor thermal stability and flamm-
ability hazards [9–11]. Until now, tremendous efforts have been de-
voted to overcoming these limitations, such as modification of
polyolefin with ceramic powders and/or other thermostable polymers
[12,13], fabrication of nonwoven-based or unique structure composite
separators [14–16]. Nevertheless, there are still limitations for practical
applications owing to costly and complicated procedures as well as
weak bonding forces between the matrix and the modifier. There is no
doubt that there needs to be further development of functional high-
performance separators.
tional fibrous separators with controllable compositions and structures
[14,17–19], in addition that electrospun nanofibrous separators possess
an interconnected porous structure, high porosities and air perme-
ability. Thus, they are able to uptake large amounts of liquid electro-
lytes and offer effective conduction channels, which in turn are en-
dowed with high ionic conductivity and good electrochemical
properties [20]. Moreover, the diameters of fibers in electrospun
membranes would also play crucial roles on the equivalent/apparent
pore sizes and even on the LIB separator performances [21]. Based on
these characteristics, nanofiber-based separators including polyimide
[22] polyacrylonitrile [21], polyethylene terephthalate [23], poly-
vinylidene fluoride (PVDF) and its copolymer [24–26] have been
widely studied. Particularly, PVDF has attracted considerable attention
because of its high affinity with nonaqueous electrolytes, good film-
forming properties, outstanding thermal stability and electrochemical
stability. However, PVDF-based separators suffer from low ionic con-
ductivity because of high crystallinity of PVDF [27]. Attempts to solve
this problem have included innovative polymer synthesis [28],
blending with other polymers [29] and fabrication of composite
polymer electrolytes by addition of inorganic fillers [30]. Of all the
mentioned techniques, blending has been identified as a simple and
effective method, which is easy to control the composition and

⁎
Corresponding author.
E-mail address: hfxiang@hfut.edu.cn (H. Xiang).

https://doi.org/10.1016/j.memsci.2018.11.041
Received 17 August 2018; Received in revised form 14 November 2018; Accepted 19 November 2018
Available online 20 November 2018
0376-7388/ © 2018 Elsevier B.V. All rights reserved.
L. Wang et al.
structures of the composite separators. For example, poly(ethylene
oxide) (PEO)/PVDF [31] blends can obviously improve the pore con-
figuration of separators, and obtain higher ionic conductivity up to 2
mS cm−1. PVDF/poly(vinyl chloride-co-vinyl acetate) blended separa-
tors can suppress the crystallinity of PVDF and possess good electro-
chemical properties [32].
Poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE)
is a semi-crystalline polymer with a reduced crystallinity degree by
introducing the chlorotrifluoroethylene segments. PVDF-CTFE usually
shows high electromechanical response, high flexibility, high elonga-
tion and cold impact resistance in comparison of other copolymers of
PVDF [33,34]. Moreover, the halogen elements F, Cl in PVDF-CTFE can
improve the safety of separators, because they (especially Cl) have the
flame-retarding function. It is well-known that introduction of ceramic
nanoparticles can not only improve mechanical strength, thermal sta-
bility of separators, and also enhance the electrochemical performance
of LIBs [12,35]. Moreover, the performance of nanofibrous separators
can be further improved by Al2O3 [35], SiO2 [12] and other ceramic
particles [36–38] to fabricate an organic-inorganic hybrid structure.
Nevertheless, these inorganic ceramic particles have negligible effect on
the flame-retarding property of the separators. Sb2O3 is one of the
earliest flame retardants, and it exhibits synergistic flame retardancy
with Cl element [39,40]. The flame retardant properties exhibited by
SbOCl are most certainly as a result of its thermal decomposition to
evolve SbCl3 gas, which is an efficient fire inhibitor. SbOCl comes from
Sb2O3 and halogen-containing compounds, and then the flame-re-
tarding SbCl3 gas can be released in the following reactions [41]. After
the battery encounters a fire, the released SbCl3 gas can retard or ex-
tinguish the combustion of the battery.
5 SbOCl(s)→Sb4O5Cl2(s)+SbCl3(g) 250–280 °C (1)
4 Sb4O5Cl2(s)→5 Sb3O4Cl(s)+SbCl3(g) 410–475 °C (2)
3 Sb3O4Cl(s)→4 Sb2O3(s)+SbCl3(g) 475–565 °C (3)
In this work, we develop a Sb2O3 modified PVDF-CTFE fibrous se-
parator via an electrospinning technique. Without Sb2O3 modification,
the PVDF-CTFE electrospun fibrous membrane has excellent thermal
stability and wettability toward nonaqueous electrolyte compared to
the commonly used polyethylene (PE) separator. But its mechanical
strength and flame-retarding property are not satisfying. When 2%
Sb2O3 nanoparticles are introduced to modify the PVDF-CTFE mem-
brane, an organic-inorganic composite membrane denoted as SPCF is
obtained. As a result, the SPCF composite membrane exhibits excellent
electrolyte uptake, high ionic conductivity, good thermal stability, en-
hanced mechanical strength and improved flame-retarding property,
leading to outstanding performance of Li||LiFePO4 cells (Fig. 1).
2. Experimental section
2.1. Preparation of the SPCF membrane
The SPCF membrane was prepared by the electrospinning method.
First, PVDF-CTFE (VDF/CTFE = 91/9 in molar ratio, Solvay 31508)
was dried at 80 °C for 24 h before use, and then dissolved in N,N-di-
methyl formamide (DMF) to form a solution with the concentration of
20%. The solution was mechanically stirred at 60 °C for 12 h to obtain a
uniform solution. Second, the Sb2O3 nanoparticles (20–40 nm, Fig. S1)
with the mass ratio 2% of the PVDF-CTFE above were dispersed in the
solution by ball-milling treatment for 3 h and ultrasonically agitated for
0.5 h to form a spinning solution. The as-prepared solution was then
electrospun into fibers at a flow rate of 33.6 mL min−1, a voltage of
12 kV, and a tip-to-collector distance of 25 cm. Subsequently, the col-
lected SPCF electrospun fibrous membranes were drying under vacuum
of 80 °C for 24 h to ensure the removal of all residual solvent. For
comparison, the PCF membranes were prepared in a similar procedure
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Journal of Membrane Science 572 (2019) 512–519
just without the introduction of Sb2O3 nanoparticles.
2.2. Characterization of the SPCF membrane
The morphology of the SPCF fibrous membrane was performed by a
field emission scanning electron microscopy (FESEM, Hitachi SU8020)
and a transmission electron microscopy (TEM, HT7700). The thick-
nesses of various membranes were measured by a micrometer. The
mechanical strength of the membranes was measured with a DMAQ800
dynamic mechanical analyzer (TA Instruments) using a mini-tensile
bar, and the tests to measure the stress-strain relationship were carried
out at room temperature. The porosities of the separators were de-
termined by using n-butanol uptake tests. As described in our previous
paper [42], the porosity of each separator was calculated in the fol-
lowing Eq. (4):
Ww −Wd
Porosity(%) = × 100%
ρb V (4)
Where Ww and Wd are the weights of wet and dry separator, respec-
tively; ρ b is the density of n-butanol, and V is the geometric volume of
the separator. The electrolyte wettability of separators was determined
by contact angles test. The contact angles between separators and the
electrolyte were tested by a contact angle tester (DSA10-Mk2, KRUSS
Gmbh Germany). The electrolyte uptake (U) was calculated according
to the following equations [32]:
W1 −W0
U (%) = × 100%
W0 (5)
where W1 and W0 are the weights of a membrane before and after being
soaked in an electrolyte of 1 mol L−1 LiPF6/ethylene carbonate (EC)
+ diethyl carbonate (DEC) (1:1, w/w) for 2 h in an Ar-filled glove box
(MBraun), respectively.
The melting temperatures (Tm) of the membranes were measured
using a differential scanning calorimeter (DSC) (Q20, TA Instruments-
Waters LLC) and each sample was scanned from −60–200 °C at a
heating rate of 10 °C min−1 under a nitrogen atmosphere. The thermal
stabilities of the membranes were determined by thermal shrinkage
tests at 160 °C for 2 h.
A GOVMARK MCC-2 Microscale Combustion Calorimeter (MCC)
was used to investigate the combustion behaviors of the membranes,
according to previous literature [43]. In each MCC test, about 5 mg
membrane samples were heated to 700 °C at a rate of 60 °C min−1 at a
N2 flow rate of 80 mL min−1. The volatile thermal decomposition pro-
ducts were mixed with an O2 flow rate of 20 mL min−1 followed by
entering a 900 °C combustion room. The heat release rate dQ/dt (W)
and sample temperature as a function of time at a constant heating rate
can be measured. The specific heat release rate HRR (W g−1) was
calculated by dividing dQ/dt at each point in time by the initial sample
mass. A derived quantity, the heat release capacity HRC (J g−1 K−1)
was obtained by dividing the maximum value of the specific heat re-
lease rate by the heating rate. The heat release capacity is a molecular-
level flammability parameter, which is a good predictor of flame re-
sistance and fire behavior. The TG-FTIR technique coupling thermo-
gravimetric (TG) analyzer (TGA-Q5000, TA Co., USA) and Fourier
transform spectrometer (FTIR, Nicolet 6700), was carried out to in-
vestigate the thermal decomposition mechanism of the membranes. The
TG analysis of 10 mg sample was carried out by heating (20 °C min−1)
at a N2 flow rate of 35.0 mL min−1.
2.3. Electrochemical performance measurements
The ionic conductivities of the separators immersed with the elec-
trolyte were determined by ac impedance spectroscopy over a range
from 100 kHz to 0.1 Hz. In order to obtain the ac impedance, the cell
with an electrolyte-immersed separator sandwiched into two parallel
stainless steel (SS) electrodes was tested on a CHI660 electrochemical
L. Wang et al.
Fig. 1. Preparation and schematic view of SPCF nanofibrous membrane.
workstation (Shanghai Chenhua). The ionic conductivity (σ ) was cal-
culated by the following Eq. (6) [44]:
d
σ=
Rb × A (6)
where Rb is the bulk resistance from ac impedance; d and A are the
thickness and the effective area of the separator, respectively.
The cell performance of the Li||LiFePO4 CR2032-type coin cells
using various separators was tested between 2.5 and 3.8 V on a Land
battery cycler. The LiFePO4 cathode was prepared by coating the mixed
slurry of LiFePO4, conductive carbon additive (Super-P, TIMCAL) and
PVDF (Solvay 5130) (84:8:8, w/w/w) in N-methyl-2-pyrrolidinone
(NMP) onto a high-purity aluminum foil. After drying and pressing, the
received laminate was punched into discs (Φ14 mm) as the LiFePO4
electrode for assembling coin cells. The mass loading of LiFePO4 was
controlled at around 2.5 mg cm−2. High purity Li foil was used as the
counter and reference electrode in the Li||LiFePO4 cells. All the cells
were initially cycled twice at 0.1 C (1 C = 150 mA g−1) for activation.
The cycling performance was measured at 1 C and rate capabilities were
obtained at different current densities ranging from 0.5 to 32 C for
charging and discharging. The interfacial compatibility with the Li
electrode after 100 cycles was determined by electrochemical im-
pedance spectra (EIS) on the CHI660 electrochemical workstation at a
frequency range from 100 kHz to 1 Hz.
3. Results and discussion
In order to investigate the morphologies of the PCF and SPCF
composite membranes, SEM analysis was performed and compared
with the morphology of the PVDF membrane (Fig. S2). As shown in
Fig. 2a-d, the PCF and SPCF membranes show highly uniform porous
fibrous networks with the diameters of 300–400 nm. The surface of PCF
nanofibers is smooth, while some Sb2O3 nanoparticles are lying on the
PCF nanofibers to make the surface of SPCF nanofibers rougher. Due to
the porous fibrous networks, the porosities of the PCF and SPCF
membranes are approximately twice as that of the PE separator
(Table 1). For separator applications, the high porosity is necessary for
allowing fast ion transportation between two electrodes. Moreover,
Fig. 2e shows that most Sb2O3 nanoparticles are inside the nanofibers
and little are on the surface of nanofibers. These ceramic nanoparticles
can effectively improve mechanical properties of membranes [45].
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Journal of Membrane Science 572 (2019) 512–519
Thus, the SPCF membrane here has great opportunities to increase
mechanical strength compared to the PCF membrane. Fig. 2f shows the
stress-strain curves of PCF and SPCF membranes in the machine di-
rection, compared with the commercial PE membrane. The maximum
stress and strain of the PCF membrane are about 4.6 MPa and 87.5%,
while those of the SPCF membrane are about 13.5 MPa and 141.1%.
These improved mechanical properties are attributed to the Sb2O3
ceramic nanoparticles inside the nanofibers (Fig. 2e). Due to the porous
fibrous networks of the SPCF membrane, the maximum stress of the
SPCF membrane are relatively lower than those of the PE membrane
(62.3 MPa), while the SPCF separator still meets the requirements for
the battery production.
The wettability of membranes was evaluated by the electrolyte
contact angle test, and the results are shown in Fig. 3a-c. The PCF and
SPCF composite membranes were quickly wetted by the electrolyte
with a contact angle of 0 °, while the PE membrane was hardly wetted
fully by the electrolyte with a contact angle of 38.8°. It can be explained
that the nonpolar PE membrane has intrinsically poor wettability with
the commercial nonaqueous electrolytes [46]. The superior electrolyte
wettabilities of the PCF and SPCF electrospun membranes are attributed
to their porous fibrous networks. Moreover, the Sb2O3 nanoparticles
lying on the fibrous surface also help to increase electrolyte wettability
due to the affinity of Sb2O3 towards electrolyte components [47].
Moreover, the electrolyte uptakes of the PCF and SPCF composite
membranes were larger than that of the PE separator. As shown in
Table 1, the electrospun PCF and SPCF membranes have relatively
higher electrolyte uptakes of 340% and 356%, respectively, than the PE
membrane (80%). Especially, some Sb2O3 nanoparticles lying on the
SPCF nanofibrous surface (Fig. 2d-e) not only enhance surface rough-
ness, but also form extensive Lewis acid/base interactions with the
electrolyte components [13]. These results of electrolyte uptakes are
well accordance with the contact angle testing. Since it has excellent
electrolyte wettability, the SPCF composite membrane is expected to
provide higher ionic conductivity than the PCF and PE membranes. The
Nyquist curves of the SS= |SS cells using the electrolyte-soaked se-
parators in Fig. 3d confirm the higher ionic conductivity of SPCF
membrane. The high-frequency intercept on the Z′ axis usually re-
presents the bulk resistance Rb of the separators in the electrolyte.
Obviously, the bulk resistance of SPCF composite membrane is lower
than the PCF and PE membranes. According to the Eq. (6) mentioned
above, the ionic conductivity of the SPCF membrane is calculated to be
L. Wang et al. Journal of Membrane Science 572 (2019) 512–519

Fig. 2. SEM images of the electrospun PCF membrane (a, b) and the SPCF composite membrane (c, d). TEM image of SPCF nanofibrous (e). Stress-strain curves of the
PCF membrane and SPCF composite membrane in comparison with commercial PE membrane (f).

2.88 mS cm−1, which surpasses those of the PCF (2.52 mS cm−1) and
PE (0.54 mS cm−1) membranes. Therefore, the SPCF membrane can
well meet the conductivity requirement of LIB applications.
Micro-sized porous polyolefin separators often shrink at elevated
temperatures, which could lead to serious safety concerns of the bat-
tery. The thermal shrinkages of separators were observed by measuring
the area shrinkage before and after thermal exposure at 160 °C for 2 h
(Fig. 4a). Obviously, the PE separator has a significant shrinkage of 90%
after thermal exposure. However, the PCF and SPCF membranes have
almost no shrinkages, due to the good heat resistance of PVDF and its
copolymers [48]. The DSC curves of three membranes were collected as
shown in Fig. 4b. The PE separator shows an endothermic peak at

Table 1
Physical properties of the PE, PCF and SPCF membranes.
Separator Thickness (μm) Porosity (%) Electrolyte uptake (%) Resistance (ohm) Ionic conductivity (mS cm−1)

PE 16 40 ± 3 85 ± 5 1.47 0.54
PCF 42 ± 5 70 ± 3 340 ± 10 0.89 2.52
SPCF 42 ± 5 72 ± 3 356 ± 10 0.67 2.88

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Fig. 3. Contact angles for the PE membrane

(a), the PCF membrane (b) and the SPCF
composite membrane (c) with the electrolyte.
Nyquist plots of the electrolyte-soaked PE, PCF
and SPCF membranes in the SS= |SS cells (d).

Fig. 4. (a) Photographs of the PE, PCF and SPCF composite membranes before and after thermal exposure at 160 °C for 2 h; (b) DSC curves of the PE, PCF and SPCF
membranes.

around 135 °C indicating the melting point of PE, while the PCF and
SPCF membranes shows an endothermic peak at 172 °C, which is the
typical melting temperature of PVDF-CTFE. Evolution of open-circuit
voltages of fully charged Li||LiFePO4 cells using the SPCF separator at
60 °C demonstrates good thermal stability of the SPCF membrane (Fig.
S3) at elevated temperature.
Flame retardancy of the separator is very important for LIBs to
improve battery safety. Herein, the non-flammability of the membranes
was evaluated on an oxygen-consumed MCC. Heat generation and re-
lease rates can be received from complete combustion of the released
gases during the controlled pyrolysis of the membrane samples.
Compared to PVDF (Fig. S4), the PCF membrane holds smaller heat
release rate indicating the better flame retardancy of PVDF-CTFE. As
shown in Fig. 5, the addition of Sb2O3 can greatly decrease the heat
Fig. 5. MCC curves and data of various membranes. HRC: Heat release capacity
release rate of PVDF-CTFE. Moreover, the SPCF membrane exhibits the (J g−1 K−1); THC: Total heat of combustion (kJ g−1).
relatively lower heat release capacity (HRC) and total heat of com-
bustion (THC) than the PE and PCF membranes, which is attributed to
synergistic flame retardancy by Sb2O3 and F, Cl in the PVDF-CTFE. Red- S5 also verified the interactions between Sb2O3 nanoparticles and
shift (to low wavenumber) of Sb-O bonds in the SPCF membrane in Fig. PVDF-CTFE polymer chains [40,49]. The Lewis acid-base reaction

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Fig. 6. The 3D surface graph for the FTIR spectra of the evolved gases produced by the PCF separator (a) and the SPCF separator (b); Gram−Schmidt release curves
of the PCF and SPCF separator (c); IR spectra of them at 23.6 min (d).
between Sb2O3 and PVDF-CTFE can form the flame-retarding SbCl3(g)
product [41]. This non-flammability would play a significant role on
terminating fire or other accidents under abuse conditions, and finally
enhance the safety characteristics of LIBs.
TG-FTIR coupling technique is used to understand the thermal de-
composition mechanism of membranes. TG curves in Fig. S6 indicate
that introduction of Sb2O3 nanoparticles can effectively suppress
thermal decomposition of the SPCF membrane. Figs. 6a and 6b show
the 3D surface graphs for the TG-FTIR spectra of the gases evolved by
the PCF and the SPCF membranes, respectively. Obviously, the gas
decomposition products of the PCF membrane are different from those
of the SPCF separator. This further indicates their different thermal
decomposition mechanism between the SPCF and PCF membranes. As
shown in Fig. 6c, the addition of Sb2O3 greatly decreases the total
pyrolysis gaseous products. FTIR spectra at 23.6 min in Fig. 6d show the
main difference of the absorption bands at 3400–4000 cm−1, which
suggests that Sb2O3 in the SPCF membrane facilitates the production of
H2O during the pyrolysis [50]. Therefore, the combination of Sb2O3 and
PVDF-CTFE can obtain synergistic effect on the suppression of gaseous
products generation and production of H2O.
Li||LiFePO4 cells were used to evaluate the cell performance of the
PCF and SPCF membranes as separators compared with the PE se-
parator. The SPCF separator has good electrochemical stability in
Li||LiFePO4 cells, and even the better electrochemcial oxidation stabi-
lity than the PE and PCF separators (Fig. S7). As shown in Fig. 7a, the
initial discharge capacity of Li||LiFePO4 cell using the PCF separator is
162 mAh g−1, which is higher than that using the PE separator (153
mAh g−1). Usually, electrospun nanofibrous membrane has higher
porosity and electrolyte uptake, which exhibits lower internal re-
sistance and higher capacity. After Sb2O3 nanoparticles were in-
troduced, the initial discharge capacity of the Li||LiFePO4 cell using the
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Journal of Membrane Science 572 (2019) 512–519
SPCF separator increases to 172 mAh g−1 because the filler-polymer
interaction (Fig. S5) do help to reduce the polarization of the cell (Fig.
S8). Fig. 7b shows cycling performance of the cells using three types of
separators at 1 C. For the cells using the PCF and SPCF separators, no
apparent capacity loss is observed after 100 cycles at 1 C, while the cell
using the PE separator exhibits a relatively apparent capacity decline
after 100 cycles. Specifically, the cell with the SPCF separator has
higher discharge capacity (167 mAh g−1) than the cells with the PCF
separator (157 mAh g−1) and the PE membrane (138 mAh g−1) after
100 cycles. Fig. 7c shows the rate capability of the cells containing
various separators. The cell with the SPCF separator has slightly higher
capacities compared to the PE membrane and PCF membrane at the
same C rates. More importantly, the cells containing the SPCF separator
exhibits less capacity fading when the C rate increases. At 32 C, the cell
containing the PE separator has the lowest discharge capacity of 19
mAh g−1, while the discharge capacity increases to 93 mAh g−1 when
the SPCF separator is used. The excellent rate performance of the cell
using the SPCF separator is attributed to its high ionic conductivity, low
interfacial resistance and good electrochemical stability (Fig. S7).
Herein, most results of the SPCF separator are better than those of
previous PVDF-based separators [51–56], as shown in Table 2. From
Fig. 7d, the cell using the SPCF separator exhibits the lowest cell re-
sistance, which is consistent with its superior rate performance. These
results confirm that Sb2O3 modified electrospun PVDF-CTFE nanofi-
brous membranes are promising separator candidate for rechargeable
LIBs.
4. Conclusion
A Sb2O3 modified PVDF-CTFE fibrous (SPCF) membrane has been
prepared via an electrospinning technique. On one hand, the SPCF
L. Wang et al. Journal of Membrane Science 572 (2019) 512–519

Fig. 7. Li||LiFePO4 CR2032-type coin cells performance using the PE membrane, PCF membrane and SPCF membrane, respectively. (a) Initial charge/discharge
voltage profiles at 1 C, (b) cycling performance at 1 C, (c) rate capability, (d) ac impedance after 100 cycles.

Table 2 Foundation of China (Grant Nos. 20676067, 51372060, 21676067, and

Comparison on properties of various different PVDF and copolymers composite 21606065), Anhui Provincial Natural Science Foundation (Grant No.
separators. 1708085QE98), and the Fundamental Research Funds for the Central
Membrane Porosity (%) Conductivity (mS Capacity Ref. Universities (Grant No. JZ2017HGTB0198, JZ2017YYPY0253).
materials cm−1) (mAh·g−1)
Appendix A. Supporting information
PVDF 75.8 3.01 108 (1 C) [51]
PVDF 20 0.23 56 (2 C) [52]
PVDF 78.7 3.32 110 (5 C) [53]
Supplementary data associated with this article can be found in the
PVDF 80 1.72 110 (5 C) [47] online version at doi:10.1016/j.memsci.2018.11.041.
PVDF-HFP – 9 139 (1 C) [54]
PVDF-HFP 78 1.03 145 (0.5 C) [55] References
PVDF-CTFE 60 1.5 117 (1 C) [33]
PVDF-CTFE 74 0.8 89 (8 C) [56]
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