Journal of Membrane Science 675 (2023) 121533

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Journal of Membrane Science

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

Mussel stimulated modification of flexible Janus PAN/PVDF-HFP nanofiber

hybrid membrane for advanced lithium-ion batteries separator
Mao Guo a, Jing Xiong a, Xuanyang Jin a, Shengjun Lu a, **, Yufei Zhang a, ***, Jian Xu b,
Haosen Fan a, *
a
College of Materials Science and Metallurgy Engineering, Guizhou University, Guiyang, 550025, China
b
Institute of Low-dimensional Materials Genome Initiative, College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, 518060, China

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

Keywords: Bicomponent polyacrylonitrile/Poly(vinylidene fluoride-co-hexafluoropropylene) (PAN/PVDF-HFP) Janus

M-PAN/PVDF-HFP nanofibers based hybrid membrane was successfully prepared by parallel electrospinning technology. Subse­
Janus nanofibers quently, modified PAN/PVDF-HFP hybrid membrane (M-PAN/PVDF-HFP) was further fabricated via mimicking
Electrospinning
the adhesive of mussel by coating dopamine alternative through polymerization of catechol and tetraethylene­
Flexible
pentamine (TEPA) in weakly alkali solution. M-PAN/PVDF-HFP maintains the abundant pore structure of the
Separator
electrospun hybrid membrane and further provides excellent electrolyte infiltration with high porosity (82.09%)
and outstanding electrolyte retention (553.23%). Simultaneously, the mechanical strength of the separator was
significantly improved (14.36 MPa). Electrochemical studies displayed that the M-PAN/PVDF-HFP composite
membrane delivered superior ion conductivity (2.81 mS/cm) and wide electrochemical stability window (~5.25
V). The cell assembled by M-PAN/PVDF-HFP separator presented outstanding rate capability with high specific
capacity of 147 mAh/g at 1 C and excellent cycle stability with discharge capacity of 120 mAh/g at 1 C after 600
cycles. Furthermore, M-PAN/PVDF-HFP separator exhibited ultra-flexibility with remarkable electrochemical
performance after repeated bending for 500 to 1000 time. This work provides new insights into polyamine
modified hybrid membranes for the potential practical applications in lithium-ion batteries separator.

1. Introduction commercial polyolefin separators.

The great crisis from excessive consumption of fossil fuels and
climate change have been gradually becoming the enormous challenge
of the world due to the huge carbon emissions. To achieve the goal of
green and low-carbon development, vigorous development of new en­
ergy sources such as secondary batteries and hydrogen energy from
electrolysis of water become the research hot spot [1–6]. Among various
secondary batteries, lithium-ion batteries (LIBs) present the advantage
of high energy density, no memory effect, low self-discharge, long cycle
life and low cost in the field of new energy field and have been widely
used in new energy vehicles, portable computers, electronic medical and
other energy storage devices [7,8]. Although the LIBs technologies are
becoming more and more attractive, many safety accidents of electric
vehicles burning and explosion have frequently happened owing to the
insufficient mechanical strength and imperfect thermal stability of the
Therefore, it is urgent to develop high-performance and satisfy sep­
arators with high porosity, good electrolyte wettability, excellent me­
chanical strength and thermal stability to satisfy the ever-increasing
market requirement of high-energy LIBs.
Electrospinning technology have been extensively used to develop
advanced LIBs separator with high energy density, which possess the
advantage of high porosity, large specific surface area, ascendant elec­
trolyte infiltration and excellent electrochemical performance [9,10].
To date, various polymer such as polyacrylonitrile (PAN) [11,12], pol­
yimide (PI) [13,14], cellulose [15,16], poly(vinylidene fluoride) (PVDF)
[17,18] and their derivatives were prepared by electrospinning tech­
nology and applied as advanced separator for LIBs. For example, Dong
et al. prepared porous PAN nanofibers membrane with different surface
and internal structures using electrospinning and phase separation
technology by mixing N–N-dimethylformamide (DMF) and

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: sjlu@gzu.edu.cn (S. Lu), yfzhang@gdut.edu.cn (Y. Zhang), hsfan@gzhu.edu.cn (H. Fan).

https://doi.org/10.1016/j.memsci.2023.121533
Received 17 January 2023; Received in revised form 12 February 2023; Accepted 26 February 2023
Available online 27 February 2023
0376-7388/© 2023 Elsevier B.V. All rights reserved.
M. Guo et al.
Tetrahydrofuran (THF) solutions with different concentrations. Micro­
porous structures could be formed in the fibers inside and out from
electrospinning process, which significantly increased porosity (67.7%)
and ion conductivity (1.96 mS/cm) of the separator [19]. Liang et al.
proposed a PVDF membrane obtaining from electrospinning and post
hot pressing process. The porosity of the PVDF membrane decreased
slightly after heat treatment, but the mechanical strength of the mem­
brane was significantly improved. In compared with commercial sepa­
rators, the PVDF membrane after heat treatment displayed wider
operating voltage window (~4.8 V) and lower bulk resistance (93.5 Ω)
[20]. However, the single component electrospun separators are still
faced with the defects of low mechanical strength, poor thermal stability
and low ionic conductivity. Therefore, bicomponent or multicomponent
composite membranes were proposed to meet the actual demand of
electrospun membranes for LIBs. Wei et al. employed coaxial electro­
spinning to produce a heat-induced shutting separator with high heat
sensitivity. As a biodegradable aliphatic polyester, Polybutylene succi­
nate (PBS) presents lower melting point than that of PE. The shell
structure of PBS in core-shell fiber could endow the PAN@PBS com­
posite membrane excellent thermal sensitivity. PAN could be used as the
core structure of composite membrane to expand the thermal closure
window of the fiber due to its superior thermal stability. At the same
time, the PAN@PBS composite membrane also exhibited eminent elec­
trolyte wettability and ionic conductivity [21]. Chen et al. prepared an
environmentally friendly PVDF/Triphenyl phosphate (TPP)/Cellulose
acetate (CA) electrospun separator. The PVDF/TPP/CA membrane dis­
played superior porosity, higher electrolyte uptake, and better thermal
stability and flame retardancy than the commercial PE separator. Cel­
lulose delivered excellent electrolyte retention ability and high pyrolysis
temperature (~ 270 ◦ C), which endowed cellulose based hybrid mem­
brane excellent thermal stability. Therefore, CA could be used to
improve the ion transport rate and thermal properties of PVDF mem­
brane. At the same time, TPP is a commonly used flame retardant, and
introducing TPP could manufacture a flame-retardant separator [22].
Recently, the strategy of Polydopamine (PDA) modified electrode
materials and separators have been widely used to improve electrical
conductivity, electrolyte infiltration and ionic conductivity [23–28].
Cao et al. prepared electrospun PVDF membrane with PDA coating on
the surface, which not only maintained the structure of PVDF nanofiber
membrane, but also increased the hydrophilicity of PVDF nanofiber
membrane with promoting Li+ transport [29]. Gao et al. prepared a
PDA@PAN separator by spin coating and electrospinning. The surface of
PAN fibers became rough and its diameter increased due to the coating
of PDA, but it inhibited the formation of lithium dendrites through
uniform distribution of Li+ flux. PDA modified layer not only increased
the ionic conductivity of separator (1.39 mS/cm), but also formed more
adhesive structures, which enhanced the physical properties of sepa­
rator [30]. The PDA presented the advantage of extreme adhesion and
could significantly improve the hydrophilicity of the material surface.
However, the high cost of dopamine significantly increased the cost of
LIBs. Therefore, the search of dopamine alternative with economic value
is urgent for LIBs separator.
Herein, self-polymerization of catechol and TEPA was selected to
simulate the modification process of dopamine to prepare a high ionic
conductivity separator. Initially, heat-resistant material PAN and high
mechanical strength polar polymer PVDF-HFP were chosen to prepare
an excellent two-component Janus nanofibers based composite mem­
brane by parallel electrospinning technology. PVDF-HFP significantly
enhanced the mechanical strength of the hybrid membrane in compar­
ison of pure PAN films. Then, the M-PAN/PVDF-HFP composite mem­
brane was further obtained by the self-polymerization of catechol and
TEPA, which presented superior electrolyte infiltration and low bulk
resistance. When used as separator of LIBs, M-PAN/PVDF-HFP hybrid
membrane displayed remarkable electrochemical performance and
provided a potential application in the commercial use of LIBs system.
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Journal of Membrane Science 675 (2023) 121533
2. Experimental section
2.1. Materials
PAN (Mw = 150 000) and n-Butanol were purchased from Macklin.
PVDF-HFP (solef 21510) was provided by Dongguan Zhanyang polymer
material Co., Ltd. Catechol, TEPA, DMF (99.5%), Tris(hydroxymethyl)
aminomethane, and N-methyl-pyrrolidone (NMP) were supplied by
Aladdin. PVDF, lithium metal, Lithium iron phosphate (LiFePO4), car­
bon black, Celgard 2325 separator, and 1 M LiPF6 electrolyte (EC: DMC:
EMC, 1:1:1 wt%) were purchased from Guangdong Canrd New Energy
Technology Co., Ltd.
2.2. Fabrication of PAN/PVDF-HFP composite membrane
PVDF-HFP with optimum concentration of 18% was acquired by
adding PVDF-HFP powder into mixed solution (DMF: acetone, 7: 3 wt
%), and an appropriate amount of PAN powder was dissolved in DMF
solvent to form 10% PAN spinning stock solution. The PAN/PVDF-HFP
hybrid membrane was manufactured by parallel electrospinning tech­
nology. The PAN and PVDF-HFP solutions were divided into two
different syringes, and the electrospun film was collected on a roller 20
cm away from the needles with voltage of 15 kV during the electro­
spinning process. Simultaneously, the optimum feeding rates of PAN and
PVDF-HFP solutions were set to 0.6 mL/h and 1 mL/h, respectively.
2.3. Preparation of M-PAN/PVDF-HFP hybrid membrane
The above-mentioned PAN/PVDF-HFP complex membrane was first
rinsed in ethanol for 5 min, and then dried for further use. The clean
composite membrane was immersed in 10 mM Tris-HCl buffer solution
(pH = 8.5) containing TEPA (5 mM) and Catechol (5 mM) for 24 h, then
the separator was taken out, and washed several times with ethanol to
remove residual polymerization products. After that, the obtained M-
PAN/PVDF-HFP composite membrane was dried at 60 ◦ C.
2.4. Characterization
The microscopic morphologies of electrospun membranes were
examined by scanning electron microscope (SEM, ZEISS Gemini 300).
The chemical composition of the membrane surface was determined by
the Fourier-transform infrared (FTIR) spectroscopy (Nicolet iS50) and X-
ray photoelectron spectrometry (XPS, Thermo Scientific K-Alpha). The
thermal contraction behaviors of Celgard 2325 separator and the M-
PAN/PVDF-HFP membrane were observed by exposing membranes at
the specific temperature for 30 min. Synchronous thermal analyzer (TG-
DSC, Mettler TGA/DSC3+) and thermogravimetric analysis (TGA, TG
209 F1 Libra, Netzsch) were performed to further investigate the ther­
mal behavior of the membranes. DSC thermograms were recorded under
N2 with 10 ◦ C/min from 100 to 400 ◦ C, and TG results were analyzed
from 30 to 800 ◦ C with heating rate of 10 ◦ C/min under N2 atmosphere.
The separator was made into 10 mm × 50 mm sample, and the sample
was tested by electronic universal testing machine (WANCE-104B) at a
tensile speed of 20 mm/min.
The weighing method was applied to measure the electrolyte uptake
of separator by calculating the weight before and after the separator
absorbed the electrolyte for 2 h [31]:
W2 − W1
Electrolyte uptake % = × 100% (1)
W1
Where W1 and W2 are the masses before and after the separator absorbed
the electrolyte, respectively. The absorption experiment of n-butanol
was executed to detect the porosity of separator [32], as shown below:
Porosity % =
Wb − Wa
× 100% (2)
ρn × S × d
M. Guo et al.
Where Wa and Wb are the masses of separator before and after absorbed
n-butanol, respectively. The ρn is the density of n-butanol. The d and S
are the thickness and the area of separator, respectively.
2.5. Electrochemical test
The electrochemical impedance spectra (EIS) were applied to
calculate the ion conductivity of separator by measuring stainless steel/
separator with electrolyte adsorbed/stainless steel cell at 5 mV AC
amplitude in the range of 0.1 Hz to 100k Hz on an electrochemical
workstation, as below [33]:
d at 2245 cm-1 could be attributed to the C≡N characteristic peak of PAN
σ= (3)
Rb × S
Where Rb is the bulk resistance of separator. The d and S represent the
thickness and the area of separator, respectively. Concurrently, linear
sweep voltammetry (LSV) was performed at a rate of 5 mV/s in the
voltage range of 3–6 V for Li/separator/stainless steel batteries.
The electrochemical performance was evaluated by assembling
LiFePO4/liquid electrolyte-soaked separator/Li battery. The mass
loading of LiFePO4 was about 1.24 mg cm-2 and the cathode was
composed of well mixed LiFePO4, carbon black, and PVDF in a mass
ratio of 7:2:1. The battery was charged and discharged at different
current densities (0.1C, 0.2C, 0.5C, 1 C, 2 C, 3 C, and 0.1C, per 5 cycles),
and the cycle stability was explored at 1 C current density over the
potential range of 2.5–4.2 V. Furthermore, the flexibility of the M-PAN/
PVDF-HFP membrane was evaluated by alternately bending and folding
to form various shapes. The electrochemical performance of battery with
bent M-PAN/PVDF-HFP flexible membrane was estimated by the same
method mentioned above.
3. Results and discussion
The PAN and PVDF-HFP solutions were mixed together to obtain
1ight grey solution (Fig. S1a). After standing for 12h and 24h, the
mixture presents obvious solution delamination (Figs. S1a and b). The
Fig. 1. Schematic illustration of electrospinning process of M-PAN/PVDF-HFP membrane.
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Journal of Membrane Science 675 (2023) 121533
obviously insoluble of PAN and PVDF-HFP is conducive to form Janus
structure nanofibers. Under the electric field, the two spinning stock
solutions converged into a two-component mixed Taylor cone at the end
point of the needle, and then the PAN/PVDF-HFP composite film was
collected on the roller, as shown in Fig. 1. Inspired by the adhesion of
mussel protein, the modified M-PAN/PVDF-HFP composite membrane
was obtained through by self-polymerization of TEPA and catechol,
presenting the yellow flexible membrane (Fig. 1 and 2a).
FTIR and XPS was adopted to analyze the chemical compositions of
the M-PAN/PVDF-HFP membrane, Fig. 2b FTIR results demonstrated
C–F and C–F3 stretching vibration peaks of PVDF-HFP at 840 cm-1, 875
cm-1, and 1180 cm-1, respectively [31,34,35]. Simultaneously, the peak
polymer, which proved that the two-component PAN/PVDF-HFP com­
posite membrane had been successfully prepared. Furthermore, the
peaks at 1506 cm-1 and 1670 cm-1 were derived from the vibration of
N–H and the overlap of C– – C on the aromatic ring [36,37], which
indicated that Catechol and TEPA were successfully coated on the sur­
face of PAN/PVDF-HFP membrane.
In addition, as shown in Fig. 2c, the O 1s peak of the composite
membrane was attributed to the sample after the reaction of Catechol
with TEPA. The C 1s spectrum could be divided into five peaks at 284.77
eV, 286.40 eV, 288.61 eV, 290.89 eV, and 293.47 eV, which were
attributed to C–C, C–O/C–N, C– – O, C–F, and C–F3, respectively (Fig. 2d).
The N 1s spectrum could be fitted into three peaks (Fig. 2e), the char­
acteristic peaks at 398.80 eV and 399.97 eV were assigned to C– – N and
C–N, respectively. Besides, the peak at 401.63 eV was derived from the
nitrile group of PAN. Similarly, the intense peak at 532.03 eV and the
weak peak at 533.71 eV were attributed to C– – O and C–O bonds
(Fig. 2f), respectively. XPS analysis results were in accordance with FTIR
results, indicating the successful modification M-PAN/PVDF-HFP
membrane from Catechol and TEPA.
Fig. 3a–c demonstrated the surface micromorphology of PAN, PAN/
PVDF-HFP, and M − PAN/PVDF-HFP membranes. The PAN separator
with uniform fiber was manufactured through electrospinning, which
showed smooth fibers surface and average diameter of 221 ± 26 nm
(Fig. 3a). As shown in Fig. 3b, PAN/PVDF-HFP bicomponent nanofibers
M. Guo et al. Journal of Membrane Science 675 (2023) 121533

Fig. 2. (a) The digital photo of M-PAN/PVDF-HFP hybrid membrane; (b) FTIR results of PAN, PVDF-HFP, PAN/PVDF-HFP, and M-PAN/PVDF-HFP membranes; (c)
XPS spectrum of M-PAN/PVDF-HFP composite membrane; (d-f) High-resolution C 1s, N 1s and O 1s spectra of M-PAN/PVDF-HFP composite membrane.

Fig. 3. (a-c) SEM of nanofiber membranes PAN, PAN/PVDF-HFP and M-PAN/PVDF-HFP; (d) EDS elements spectrum of M-PAN/PVDF-HFP composite separator; (e)
EDS elements mapping of M-PAN/PVDF-HFP composite separator.

4
M. Guo et al.
presented large fiber diameter (average diameter of 367 ± 48 nm).
Moreover, the surface of the M-PAN/PVDF-HFP fiber was relatively
rough and owned larger fiber diameter, with average diameter 372 ±
41 nm (Fig. 3c). This could be attributed to the modified layer coated on
the surface of PAN/PVDF-HFP nanofibers, and thickness of the modified
layer generated by Catechol and TEPA was only about 10 nm, which
would not block the pores of the separator.
As illustrated in Fig. 3d–e, C, F, N, and O four elements were detected
on the surface of the M-PAN/PVDF-HFP membrane, and the element
contents before and after membrane modification were compared. The
content ratio of C and F elements decreased after modification, and the
component ratio of N and O elements increased to a certain extent (the O
element in the unmodified separator may come from H2O or CO2 in the
air), and the increased N and O elements mainly came from Catechol and
TEPA. Meanwhile, it could be observed from Fig. 3e that F, N, and O
three elements were uniformly present on the membrane surface, which
confirmed that the polyamine modified layer was uniformly distribution
on the membrane surface.
The high porosity of separator is more conducive to the uptake of
electrolyte and the transport of Li+. The porosity of separator was
summarized in Fig. 4 and Table S1. The Celgard 2325 separator pre­
pared by dry stretching had only 43.55% porosity, while the electrospun
membrane owned rich pore structure, which showed higher porosity.
The two-component composite membrane PAN/PVDF-HFP prepared by
parallel electrospinning showed the highest porosity (85.70%), almost
twice that of the Celgard 2325 membrane. Catechol and TEPA were self-
polymerized on the PAN/PVDF-HFP membrane surface, which slightly
harmed the porosity of the modified M-PAN/PVDF-HFP composite
membrane, but it still had the high porosity of 82.09%. Consequently,
the modified layer polymerized by Catechol and TEPA could not block
the pore of the M-PAN/PVDF-HFP membrane, which could better absorb
and retain electrolyte, and provide more Li+ transmission channels to
promote Li+ migration.
The adsorption capacity of the membrane to the electrolyte is a
significant factor for the performance of LIBs. Fig. 4 and Table S1
summarized the electrolyte retention rates of Celgard 2325 separator,
PAN, PAN/PVDF-HFP, and M-PAN/PVDF-HFP electrospun membranes.
The Celgard 2325 separator presented retention rate of only 214.67%.
The electrospun PAN and PAN/PVDF-HFP membranes with abundant
pore structure exhibited excellent electrolyte retention, with electrolyte
retention rates of 467.86% and 502.32%, respectively. The M-PAN/
PVDF-HFP composite membrane exhibited higher electrolyte uptake of
553.23%. In conclusion, M-PAN/PVDF-HFP composite membrane
owned superior electrolyte uptake, which was instrumental in
improving Li+ transmission and enhancing the electrochemical perfor­
mance of cells.
Fig. 4. Porosity, electrolyte uptake, and ionic conductivity of Celgard 2325,
PAN, PAN/PVDF-HFP, and M-PAN/PVDF-HFP separators.
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Journal of Membrane Science 675 (2023) 121533
In addition, Celgard 2325 separator exhibited poor electrolyte
wettability, in which electrolyte droplets existed in a semicircular state
on the surface with no apparent change within 3 s because of the low
surface tension and porosity of commercial separator (Fig. 5a). It is
widely known that electrospun membranes possess rich pore structures,
which could improve the absorption capacity of electrolyte. Therefore,
the electrospun PAN separator presented a small contact angle, which
decreased from 32.6◦ to 17.8◦ within 3 s. After combination with PVDF-
HFP, the PAN/PVDF-HFP composite membrane exhibited better affinity
for electrolyte than that of pure PAN membrane due to the strong af­
finity for electrolyte of PVDF-HFP. The affinity for electrolyte was
further improved by M-PAN/PVDF-HFP composite separator modified
by Catechol and TEPA, and the contact angle of electrolyte was only 7.8◦
after 3 s. The lower contact angle signified that M-PAN/PVDF-HFP
separator was more hydrophily to the electrolyte, which was conducive
to enhancing electrolyte uptake. Fig. 5b–c compared the diffusion rate
and the immersion height of Celgard 2325 and M-PAN/PVDF-HFP
membrane to the electrolyte. Apparently, M-PAN/PVDF-HFP membrane
delivered the better diffusion rate in 30 s, and it expressed higher
infiltration height (38 mm) than that of Celgard 2325 separator (20
mm), which was ascribed to the lyophilic to the electrolyte of M-PAN/
PVDF-HFP composite membrane.
The thermal stability of membrane is an important parameter to
evaluate the safety of LIBs. To study the thermal stability of separator,
Celgard 2325 and M-PAN/PVDF-HFP separators were each heated at
gradient temperatures for 30 min, and their thermal stability was
analyzed by observing the thermal contraction of separators. The Cel­
gard 2325 separator experienced severe thermal contraction at 150 ◦ C,
with a shrinkage rate of up to 30% (Fig. 6a), and Celgard 2325 lost its
structural integrity in a molten state at 200 ◦ C, which could be attributed
to the low thermal stability of PP and PE. The M-PAN/PVDF-HFP
separator showed superior thermal stability at 180 ◦ C and retaining
more than 80% of the initial structure. The modified membrane also
exhibited preferable thermal stability at 200 ◦ C, retaining about 70% of
its initial structure.
It could be seen from the DSC spectrum in Fig. 6b that Celgard 2325
presented two endothermic peaks at 136 ◦ C and 162 ◦ C, corresponding
to the melting temperatures of PE and PP, respectively [25]. However,
Fig. 5. (a) Dynamic electrolyte contact angle tests of Celgard 2325, PAN, PAN/
PVDF-HFP, and M-PAN/PVDF-HFP membranes with time; (b) Photographs of
the Celgard 2325 and M-PAN/PVDF-HFP membranes after different wetting
time by electrolyte; (c) Contrast of Celgard 2325 and M-PAN/PVDF-HFP
membranes on electrolyte immersion-height.
M. Guo et al.
Fig. 6. (a) Thermal shrinkage behavior of separators at different temperature; b DSC results of Celgard 2325 and M-PAN/PVDF-HFP separators; (c-d) TGA and DTG
results of PAN, PAN/PVDF-HFP, and M-PAN/PVDF-HFP separators; (e) Stress-strain curves of PAN, PAN/PVDF-HFP and M-PAN/PVDF-HFP membranes; (f-h)
Flexible and folding performance of M-PAN/PVDF-HFP membrane.
M-PAN/PVDF-HFP composite membrane showed no obvious melting
endothermic peak, and only an exothermic peak appeared at 320 ◦ C,
because the PAN cyclization reaction occurred and the conjugated
structure was formed at this temperature [38]. DSC results were similar
to the above heat treatment results, which confirmed exceptional ther­
mal stability of the composite membrane based on PAN. In addition,
TGA was used to probe the thermogravimetric behavior of the
M-PAN/PVDF-HFP composite membrane. From Fig. 6c–d could be
observed that PAN, PAN/PVDF-HFP and M-PAN/PVDF-HFP membranes
presented similar thermogravimetric behavior and all began thermal
decomposition at 310 ◦ C. Nevertheless, PAN and PAN/PVDF-HFP
membranes reached the maximum thermal decomposition tempera­
ture of 320 ◦ C for the first time soon after the initial decomposition. The
M-PAN/PVDF-HFP composite membrane showed higher thermal sta­
bility, reaching the fastest pyrolysis temperature of 345 ◦ C for the first
time. Therefore, the modified M-PAN/PVDF-HFP composite separator
owned outstanding thermal stability, which might greatly ensure the
security of LIBs.
The separator should possess excellent porosity, electrolyte affinity,
and thermal stability, but also good mechanical strength, so that it could
withstand the stress in the battery manufacturing process. Fig. 6e
showed the low tensile strength (5.86 MPa) and elongation at break
(17.29%) of the electrospun PAN film. PVDF-HFP with high mechanical
strength could significantly ameliorate the tensile strength of the PAN/
PVDF-HFP composite membrane. Meanwhile, the mechanical properties
of the PAN/PVDF-HFP composite membrane were further enhanced
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Journal of Membrane Science 675 (2023) 121533
after Catechol and TEPA modification. The tensile strength raised from
12.78 MPa to 14.36 MPa, and the breaking elongation increased from
21.74% to 27.84%. This could be attributed to Catechol and TEPA self-
polymerize on the surface of nanofibers, thus forming more adhesive
structures. The high mechanical strength of the M-PAN/PVDF-HFP
separator satisfied the requirements of mechanical properties of sepa­
rator for LIBs. To better explore the effect of separator flexibility on the
electrochemistry and security performance of LIBs, flexible bending
experiments and electrochemical tests after membrane bending were
characterized. The results indicated that the M-PAN/PVDF-HFP com­
posite membranes displayed remarkable flexibility, which can be easily
crosswise folded, multiple folded and even folded into paper plane
(Fig. 6 f-h). The excellent flexibility of the M-PAN/PVDF-HFP composite
membrane provided more convenience and security, which could fully
satisfy the transport and assembly of batteries and provided feasibility
for practical application of the electrospun membrane.
The combustion experiment of separators under flame was also
simulated. Celgard 2325, PAN/PVDF-HFP, and M-PAN/PVDF-HFP sep­
arators were exposed to fire and the combustion process and final
product of the separators were recorded (Fig. 7 and Fig. S2). Celgard
2325 separator suddenly occurred thermal shrinkage at the moment of
contact with the flame, without any residual product after burning.
PAN/PVDF-HFP and M-PAN/PVDF-HFP separators had similar com­
bustion behaviors, showing superior thermal stability and forming res­
idues after combustion. Furthermore, compared with the PAN/PVDF-
HFP membrane, the combustion residues of the M-PAN/PVDF-HFP
M. Guo et al.
Fig. 7. Combustion test of Celgard 2325, PAN/PVDF-HFP and M-PAN/PVDF-HFP separators.
composite membrane presented fluffier carbon layer and richer pore
structure. The resulting carbon layer acts as a protective layer shield by
preventing the further penetration of oxygen and heat. In conclusion,
the M-PAN/PVDF-HFP hybrid film with perfect thermal stability and
physical properties showed great potential in the safety performance of
LIBs.
The ionic conductivity of separator is one of the important parame­
ters to measure electrochemical performance. Fig. 8a exhibited the EIS
spectra of Celgard 2325, PAN, PAN/PVDF-HFP, and M-PAN/PVDF-HFP
separators. The Celgard 2325 separator displayed the largest bulk
resistance (1.89 Ω) with the low ionic conductivity of 0.47 mS/cm. The
electrospun membrane owned abundant pore structure and provided
good wettability and retention ability for electrolyte, which was
conducive to promoting Li+ transmission. Therefore, PAN, PAN/PVDF-
HFP, and M-PAN/PVDF-HFP membranes all delivered low bulk resis­
tance of 1.13 Ω, 1.03 Ω and 0.88 Ω, respectively. The bulk resistance and
ionic conductivity of separators were summarized in Table S1 and
Fig. 8a. Compared with the Celgard 2325 separator, PAN, PAN/PVDF-
HFP and M-PAN/PVDF-HFP membranes all manifested high ionic con­
ductivity with values of 2.03 mS/cm, 2.06 mS/cm and 2.81 mS/cm,
respectively. The M-PAN/PVDF-HFP composite membrane showed the
lowest bulk resistance and the highest ionic conductivity, which indi­
cated that the modified layer of Catechol and TEPA enhanced the
interface compatibility between the separator and electrodes.
Fig. 8. (a) Nyquist plots and (b) linear sweep voltammetry of the batteries with various separators.
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Journal of Membrane Science 675 (2023) 121533
The electrochemical stability windows of Celgard 2325, PAN, PAN/
PVDF-HFP and M-PAN/PVDF-HFP membranes were determined by LSV.
The electrochemical oxidation limit is determined by the surge oxida­
tion current generated as the electrolyte is decomposed. The battery
with Celgard 2325 showed a sharp increase in oxidation current at
~4.25 V (Fig. 8b), while PAN, PAN/PVDF-HFP, and M-PAN/PVDF-HFP
separator cells all revealed a wide electrochemical stability window
(~5.25 V). In conclusion, M-PAN/PVDF-HFP composite membrane
showed excellent electrochemical stability.
The electrochemical properties of the cells with various separators
were analyzed by assembling Li metal/separator/LiFePO4 coin batteries.
The discharge capacities of cells assembled by Celgard 2325, PAN/
PVDF-HFP, and M-PAN/PVDF-HFP separators at 0.1C are 149 mAh/g,
169 mAh/g, and 170 mAh/g, respectively (Fig. 9a). Furthermore, the
discharge capacities of three cells all decreased with the increase of
current rates, but the M-PAN/PVDF-HFP composite membrane assem­
bled cell showed the highest discharge capacity at each rate. Fig. 9b–c
displayed the charge-discharge curves of cells at 0.1C and 3 C rates,
respectively. When the current increased from 0.1C to 3 C, the discharge
capacities retained by batteries with three different separators were 91
mAh/g, 102 mAh/g, and 117 mAh/g, respectively. The cell with M-
PAN/PVDF-HFP composite separator delivered the lowest specific ca­
pacity decay of 31%, in comparison with 39% and 40% from Celgard
2325 and PAN/PVDF-HFP membranes, which proved that the cell with
M. Guo et al. Journal of Membrane Science 675 (2023) 121533

Fig. 9. (a) Rate performance of batteries with various separators; (b-c) Charge-discharge curves of cells of three types of separators at rates of 0.1C and 3 C; (d-e)
Charge-discharge voltage platforms for cells assembled by Celgard 2325 and M-PAN/PVDF-HFP separators at 1 C; (f) Comparison of rate capacity of M-PAN/PVDF-
HFP composite separator and others in literature; (g) Cycle performance of batteries with Celgard 2325, PAN/PVDF-HFP, and M-PAN/PVDF-HFP separators at 1 C.

M-PAN/PVDF-HFP separator exhibited superior rate stability. Simulta­
neously, the cells with all separators showed stable charge-discharge
voltage platforms at current densities of 0.1C and 3 C. Fig. 9f demon­
strated that the M-PAN/PVDF-HFP membrane modified by Catechol and
TEPA showed excellent discharge capacity at various rates, compared
with the separators reported in the literature [21,26,29,31,36,39,40].
The M-PAN/PVDF-HFP composite membrane prepared in this work had
more advantages and could be used as a candidate material for the ideal
separator of high-performance LIBs.
The charge-discharge voltage platforms of the cells with Celgard
2325 and M-PAN/PVDF-HFP separators remained stable during the
charge-discharge cycle, but the discharge capacities of batteries
decreased gradually with the increased cycle life (Fig. 9d–e). Concur­
rently, the M-PAN/PVDF-HFP separator assembled battery showed
lower polarization due to its higher ionic conductivity. Fig. 9g showed
the cycle stability of cells with Celgard 2325, PAN/PVDF-HFP, and M-
PAN/PVDF-HFP separators. The battery with M-PAN/PVDF-HFP sepa­
rator demonstrated higher discharge discharge capacity and lower
discharge capacity attenuation (the specific capacity attenuation of the
cell per cycle was only 0.0306% after 600 cycles at 1 C). However, the
discharge capacities of cells with Celgard 2325 and PAN/PVDF-HFP
separators were only 81 mAh/g and 102 mAh/g, and their capacity
decays per cycle were 0.0551% and 0.0379%, respectively. Further­
more, the coulomb efficiency of the battery with the M-PAN/PVDF-HFP
separator was 98.20% after 600 cycles, which was much higher than the
battery with Celgard 2325 separator (94.96%). The high coulomb effi­
ciency of LIBs is beneficial to the reversibility of batteries in practical
applications. In conclusion, M-PAN/PVDF-HFP composite membrane
modified by Catechol and TEPA displayed good interface compatibility
with the electrodes, which was conducive to the transmission of Li+.
Therefore, the battery constituted by M-PAN/PVDF-HFP composite
membrane could show high discharge capacity and cycle stability.
The M-PAN/PVDF-HFP membrane still guaranteed the integrity of
the initial structure after alternately bending hundreds of times, due to
the exceptional flexibility of the membrane. As shown in Fig. 10a,
flexible membranes formed by repeated bending 500 and 1000 times
were designed, named B-500 and B-1000, respectively. The electro­
chemical testing of the batteries with flexible membranes was carried
out. The same electrochemical test was performed for the cell with
flexible membrane as battery assembled by the unbent separator.

8
M. Guo et al. Journal of Membrane Science 675 (2023) 121533

Fig. 10. (a) Diagram of the alternate bending process of separator; (b) Rate performance of batteries with M-PAN/PVDF-HFP, B-500, and B-1000 membranes; (c)
Comparison of rate performance of cells with M-PAN/PVDF-HFP, B-500, B-1000, and Celgard 2325 separators at different rates; (d) Cycle stability of cells with M-
PAN/PVDF-HFP, B-500, and B-1000 membranes at 1 C; (e) Comparison of discharge capacity with M-PAN/PVDF-HFP, B-500, B-1000, and Celgard 2325 separators at
different cycles.

Fig. 10b–c showed that the rate capacity of the batteries assembled by
the bent separators had a certain degree of attenuation, and the B-1000
battery exhibited outstanding rate stability and high discharge capacity
of 135 mAh/g, 123 mAh/g, and 95 mAh/g at rates of 0.5C, 1 C, and 3 C.
The batteries assembled by flexible membranes exhibited higher
discharge capacity than Celgard 2325 at high rates. Simultaneously, the
batteries with bent separator still displayed splendid cycle stability and
coulomb efficiency at 1 C, and the B-500 and B-1000 batteries showed
high discharge capacities of 135 mAh/g and 123 mAh/g, respectively.
Similarly, the cycle stability and capacity attenuation of the flexible
separator batteries were superior to those of the Celgard 2325 batteries.
The electrochemical performance was adversely affected by the bending
of the membrane, and the capacity attenuation increased with the in­
crease of the bending frequency. Although the discharge capacity of cell
assembled by the M-PAN/PVDF-HFP membrane had a certain attenua­
tion after bending, it still showed excellent electrochemical perfor­
mance. It was proved that M-PAN/PVDF-HFP composite membrane
obtained by parallel electrospinning technology and TEPA and Catechol
coating modification had excellent flexibility, which could satisfy the
bending during battery transport and assembly, and better ensure the
advance of cells.
4. Conclusion
In conclusion, the bicomponent PAN/PVDF-HFP composite sepa­
rator prepared by parallel electrospinning technology showed the su­
periorities of both PAN and PVDF-HFP polymers, and the high
mechanical strength of PVDF-HFP improved the mechanical strength of
the pure PAN membrane. In addition, the M-PAN/PVDF-HFP composite
membrane coated with Catechol and TEPA exhibited high porosity and
electrolyte wettability. Electrochemical tests delivered that the rate
performance and cycle stability of cells were conspicuously enhanced.
The high discharge capacity and capacity stability resulted from the fact
that the Catechol and TEPA modified layer enhanced the interfacial
compatibility between separator and electrodes and promoted the
transport of Li+. Moreover, the M-PAN/PVDF-HFP membrane displayed
exceptional flexibility, and exhibited prosperous electrochemical per­
formance after repeated bending 1000 cycles. Therefore, the M-PAN/

9
M. Guo et al.
PVDF-HFP separator was obtained by modifying with catechol and
TEPA could have bright prospects in replacing commercial batteries
separators.
CRediT authorship contribution statement
Mao Guo: Data curation, Writing original draft; Xuanyang Jin and
Jing Xiong: Investigation; Jian Xu: Formal analysis; Yufei Zhang and
Shengjun Lu: Supervision, Writing-review & editing; Haosen Fan:
Supervision, Methodology, Writing-review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This work was supported by National Natural Science Foundation of
China (52101243), “100-level” Innovative Talents Project of Guizhou
Province China ([2016] 5653), Natural Science Foundation of Guang­
dong Province (2023A1515012619) and Science and Technology Plan­
ning Project of Guangzhou (202102010373).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.memsci.2023.121533.
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