Journal of Power Sources 461 (2020) 228123

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Journal of Power Sources

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Lithium ion battery separator with improved performance via side-by-side

bicomponent electrospinning of PVDF-HFP/PI followed by 3D
thermal crosslinking
Ming Cai a, 1, Ding Yuan a, b, *, 1, Xiao Zhang a, Yi Pu a, Xiaofang Liu a, Hongwei He a, Lixue Zhang b,
Xin Ning a, **
a
Industrial Research Institute of Nonwovens & Technical Textiles, College of Textiles & Clothing, Qingdao University, Qingdao, 266071, Shandong, PR China
b
College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, 266071, Shandong, PR China

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

Keywords: Here, a novel PVDF-HFP/PI side-by-side bicomponent electrospun separator with cross-linked structure is suc­
Side-by-side nanofiber cessfully fabricated for lithium-ion batteries (LIBs). The bicomponent composite fiber not only integrates the
Electrospinning excellent characteristics of PVDF-HFP and PI, but also improves the mechanical strength of the electrospun
PVDF-HFP/PI
nonwoven and maintains a high level of porosity, up to 85.9 %. Moreover, the PVDF-HFP/PI(T) fibrous separator
LIBs separator
emerges outstanding performance, including the thermal dimensional stability (up to 200 � C), self-
Bicomponent fiber
extinguishment, high electrolyte uptake (483.5 %), good ionic conductivity (1.78 � 10 3 S/cm), wide electro­
chemical stability window (up to 4.94 V vs. Liþ/Li) and favorable interface structure. It is further confirmed by
the 3D simulation that the PVDF-HFP/PI(T) nonwoven using as the LIBs separator is beneficial to the homo­
geneous transmission of lithium ions. As a result, the coin cells with PVDF-HFP/PI(T) separator possess the best
first discharge capacity (120.41 mAh g 1) and coulombic efficiency (99.36 %) with respect to that of Cel­
gard2320 separator and cross-electrospun PVDF-HFP þ PI(T) separator. After 50 cycles, the discharge capacity of
Li/PVDF-HFP/PI(T)/LiFePO4 is found to be retained around 98.13 %, which is higher than 94.91 % of Cel­
gard2320 separator and 96.09 % of cross-electrospun PVDF-HFP þ PI(T) separator. Moreover, the coin cell using
the PVDF-HFP/PI (T) separator exhibited good discharge capacity under different discharge C-rate at 45 � C,
indicating its potential for the high-temperature safety of LIBs. In sum, the PVDF-HFP/PI(T) nonwoven with
excellent property has an application prospect in the field of LIBs separator, which also provides a reliable
strategy for designing the electrospun separator with improved performance.

1. Introduction
In recent years, many researchers have been focused on developing
the high-performance separators for different applications of recharge­
able lithium-ion batteries (LIBs), e.g. camcorders, mobile phones,
portable computers, electric vehicles, and even emerging smart grids [1,
2]. At present, the polyolefin-based porous membranes prepared by
stretching technique such as polyethylene (PE) and polypropylene (PP)
occupy the largest share of separator market [3]. However, due to the
weak electrolyte absorption capacity, low ionic conductivity and poor
thermal stability, the polyolefin-based separators were gradually unable
to meet the strict demands of rapid charge-discharge performance and
safety of LIBs [4]. Therefore, it is urgent and significant to exploit the
new LIBs separators with excellent wettability, ionic conductivity, high
temperature safety and high performance.
Currently, electrospun nonwovens have been applied to the field of
LIBs separators because of their high porosity and large specific surface
area [5–10]. In particular, the composite fibrous membranes with

* Corresponding author. Industrial Research Institute of Nonwovens & Technical Textiles, College of Textiles & Clothing, Qingdao University, Qingdao, 266071,
Shandong, PR China.
** Corresponding author. Industrial Research Institute of Nonwovens & Technical Textiles, College of Textiles & Clothing, Qingdao University, Qingdao, 266071,
Shandong, PR China.
E-mail addresses: yuanding@qdu.edu.cn (D. Yuan), xning@qdu.edu.cn (X. Ning).
1
Ming Cai and Ding Yuan contributed equally to this work.

https://doi.org/10.1016/j.jpowsour.2020.228123
Received 22 September 2019; Received in revised form 18 March 2020; Accepted 26 March 2020
Available online 18 April 2020
0378-7753/© 2020 Published by Elsevier B.V.
M. Cai et al.
Fig. 1. Schematic diagram of the side-by-side electrospinning process and SEM and fluorescence microscopy images of PVDF-HFP/PI fibers.
superior properties were developed through the design of fiber compo­
sition and structure, such as the blend spinning [11–13], the bicompo­
nent co-electrospinning [14], layer-by-layer spinning [15,16], coaxial
spinning [17,18] and side-by-side spinning [19,20] etc., making the
nonwovens exhibit more commendable performance [21,22]. Among
them, the side-by-side spinning is a simple, convenient and cost-effective
process for preparing the bicomponent composite nonwovens. The
parallel structure of the obtained fibers makes the composite fibers give
full play to the advantages of the two components [20], providing more
possibilities for the preparation of high-performance LIBs separators. In
addition, the low mechanical properties of electrospun nonwovens have
greatly limited their application in LIBs, which was mainly due to the
random accumulation and no bonding of electrospun nanofibers,
resulting in a small holding force and easy sliding [3]. It is worth noting
that both the strength and modulus of electrospun nonwovens can be
effectively improved by the post-treatment to form the bonding between
fibers (e.g. the solvent steam treatment and thermally induced
micro-crosslinking treatment) [23]. Yet, the degree of cross-linking
treatment is usually difficult to control, which is easy to block the
pores of nonwovens and lose the original high porosity.
Poly (vinylidene fluoride) (PVDF) and its copolymers, especially
PVDF-HFP, are one of the most used polymers for the fabrication of
electrospun nonwoven separators [24]. Studies have shown that the
PVDF-HFP has a high affinity for the liquid electrolyte solution and can
form a partial gel state with the electrolyte, exhibiting excellent elec­
trochemical performance [1]. Moreover, the electrode binder commonly
used in the LIBs is PVDF, so the separator prepared by PVDF can better
bind to the electrode and effectively reduce the interface resistance [24].
However, in some special cases, the separators using PVDF or its co­
polymers may shrink and cause battery safety problems owing to the
poor thermal stability. This problem can be solved by preparing the
composite fibers of high temperature resistant materials, for instance
polyimide (PI) [17,25]. The initial thermal decomposition temperature
of PI exceeds 500 � C [26], which effectively avoids the short circuit
caused by the shrinkage of Celgard and PVDF separator at 150 � C and
shows great safety. Besides, the wettability between PI and polar sol­
vents such as ethylene carbonate and dimethyl carbonate is very good,
greatly improving the retention rate of electrolyte [26,27].
In this work, the side-by-side PVDF-HFP/PI bicomponent nonwovens
2
Journal of Power Sources 461 (2020) 228123
were fabricated by electrospinning, which made full use of the advan­
tages of PVDF-HFP and PI. Subsequently, the introduction of cross-
linking points in the membrane strengthened the physical overlap
structure between the fibers and effectively improved the mechanical
strength of electrospun nonwoven. More than this, due to the structural
and component advantages of the side-by-side bicomponent fibers, the
post-treated nonwoven PVDF-HFP/PI(T) showed the high porosity (85.9
%), electrolyte uptake (483.5 %), ionic conductivity (1.78 � 10 3 S/
cm), thermal dimensional stability, self-extinguishment, electro­
chemical performance and battery performance. The 3D simulation
further indicated that the structure of the cross-linked PVDF-HFP/PI
separator was favorable for the homogeneous transport of lithium ions.
In short, the cross-linked PVDF-HFP/PI side-by-side nonwoven with
improved performance has a considerable application potential in the
field of LIBs separator.
2. Experimental
2.1. Materials
Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP, Mw
¼ 400,000, Aladdin), Polyimide resin (PI, 20 wt%, Hangzhou Plastic
UNITA Special Technology), Dimethylformamide (DMF, 98 %, Sino­
pharm Chemical Reagent), n-butyl alcohol (NBA, AR, Sinopharm
Chemical Reagent), acetone (98 %, Sinopharm Chemical Reagent),
Rhodamine B (Mw ¼ 497.01, Tianjin Keomi Chemical Reagent) and
fluorescein (Mw ¼ 332.31, Tianjin Fuchen Chemical Reagent) were used
as received without further purification. The liquid electrolyte solution
of 1 M LiPF6 in the ethylene carbonate/dimethyl carbonate (EC/DMC,
1/1, v/v) was obtained from Zhangjiagang Guotai-Huarong New
Chemical Materials. The Celgard membrane (Celgard2320, thickness:
20 μm, North Carolina, USA) was used for the comparative study.
2.2. Preparation of fibrous nonwovens
The 16 wt% homogeneous PVDF-HFP solution was prepared by
dissolving the PVDF-HFP particles in a mixed solvent DMF/acetone (1/
1, w/w) with magnetic stirring for 24 h and static placement to elimi­
nate bubbles. The side-by-side electrospinning was conducted by using
M. Cai et al. Journal of Power Sources 461 (2020) 228123

Fig. 2. SEM images and corresponding fibers diameter distribution of PVDF-HFP (a), PI (b), PVDF-HFP þ PI (c), and PVDF-HFP/PI (d) electrospun nonwovens,
respectively.

our homemade device, including a high-voltage DC supply (GAMMA, In the fluorescent labeling experiment, the fluorescent indicators
Washington DC, USA) with an applied voltage of 18 kV, two propulsion were added to different electrospinning solutions. That is, 0.5 wt%
pumps (LSP01-3A, Baoding Lange Constant Flow Pump Co., Ltd.) with a fluorescein with green fluorescence was applied to the PVDF-HFP
propelling speed of 0.5 mL/h and a homemade roller receiver with a polymer solution and 0.5 wt% rhodamine B with red fluorescence was
distance 15 cm from the syringe. Notably, the spinning conditions added to the PI solution (Fig. 1). The polymer solutions with different
mentioned above were all optimized experimental results. In the early fluorescent indicators were subjected to side-by-side electrospinning
stage, the appropriate parameters were determined by adjusting the according to the above steps. In addition, the side-by-side PVDF-HFP/PI
concentration of electrospinning solution, spinning speed (0.5 and 1 and cross-electrospun PVDF-HFP þ PI nonwovens were placed in an
mL/h), spinning voltage (15, 18 and 21 kV) and distance (15, 20 and 25 oven of 145 � C for 20 min during thermal cross-linking treatment, which
cm) during the electrospinning. Finally, the determined spinning pa­ were recorded as PVDF-HFP/PI(T) and PVDF-HFP þ PI(T), respectively.
rameters not only ensured the preparation efficiency of the side-by-side
fibers, but also optimized the fiber diameter and obtained a uniform
2.3. Characterization
pore structure.
In the electrospinning process, the PVDF-HFP and PI solutions were
The microscopic morphology and corresponding fiber diameter dis­
added to two syringes, respectively. Under the action of electric field,
tribution of the polymer membranes were investigated by scanning
the two polymer solutions converged at the needle mouth to form two
electron microscopy (SEM, Phenom, Germany). The average pore sizes
mutually contacting Taylor cones, and then the parallel fibers were
were determined according to the bubble method using aperture tester
obtained, as shown Fig. 1. As a comparison, pure PVDF-HFP and PI
(TOPAS PSM-165, Frankfurt, Germany) with a fixed testing area of 2.01
membranes were separately spun by the traditional single-nozzle elec­
cm2.The fluorescence microscope (OLYMPUS BX51, Japan) was applied
trospinning method. Besides, the mixed PVDF-HFP and PI (abbreviated
to verify the component of the PVDF-HFP/PI side-by-side fibers. Fourier
as PVDF-HFP þ PI) nonwovens were obtained through four needle cross-
Transform Infrared (FTIR, Nicolet iS5, USA) spectrometers were
electrospinning process. Specifically, the four needles cross-
employed to identify chemical composition of samples. X-ray diffraction
electrospinning was that the four syringes with the two types of poly­
(XRD) patterns of films were obtained using Rigaku SmartLab diffrac­
mer solutions were arranged alternately in a straight line to form a
tometer in the range of 10 – 60 � and at a scan rate of 3 � /min. The
composite membrane (Fig. S1) [14]. The spinning parameters of the
mechanical properties of nonwovens were measured by Instron 5300
comparative nonwovens were consistent with those of the side-by-side
Universal Strength Tester at a speed of 5 mm/min, and the size of each
fibers. All electrospinning experiments were operated at room temper­
specimen was cut into 8 � 40 mm. At least 5 groups of tests were per­
ature with a humidity control of 48 � 3 %RH. The residual solvent on
formed on each sample and the average was taken. Thermogravimetric
the nonwoven would be removed by drying at 60 � C for 24 h before use.
analyzer (TGA, 209F1 Iris, German), differential scanning calorimeter

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M. Cai et al.
Fig. 3. FTIR spectra (a) and XRD pattern (b) of PVDF-HFP, PVDF-HFP þ PI, PVDF-HFP/PI and PI electrospun nonwovens, respectively.
(DSC, Mettler Toledo) and heat treatment were carried out to evaluate
the thermal property and thermal dimensional stability. The self-
extinguishment of membranes was examined by the combustion tests.
The process was achieved by using a lighter to ignite the fiber nonwoven
(about 0.5 g) and observing the flame state of membranes after
removing the lighter.
The wettability of membrane to the electrolyte was studied by the
contact angle using a contact angle measuring instrument (JY-PHb,
China). The electrolyte uptake (EU) of membranes was calculated with
the differential weight method according to the following equation [18]:
W1 W0
EU ¼ � 100 %
W0
where W0 and W1 represent the weights of polymer membranes before
and after immersed in the electrolyte, respectively.
The porosity of membranes was determined by the n-butanol uptake
method and calculated as [18]:
P¼
WW Wd
� 100 %
ρ�V
where Wd and Ww are the weights of membranes before and after ab­
sorption of n-butanol, respectively, ρ represents the density of n-butanol
(0.8098 g/cm3), and V represents the volume of samples.
2.4. Electrochemical characterization
The electrochemical properties of the polymer nonwoven were
evaluated on an electrochemical workstation (CS350H, China). The
electrochemical stability window was measured by linear sweep vol­
tammetry (LSV) at a scan rate of 5 mV s 1 over the potential range from
3.5 to 5.5 V. AC impedance measurement was used to study the ionic
conductivity and interfacial impedance of the sample membranes,
which was conducted in the frequency range of 0.1 – 106 Hz with a
potential amplitude of 5 mV. The interfacial impedance was studied by
measuring the EIS spectra in the Li/liquid electrolyte-soaked separator/
Li cells. The ionic conductivity of the liquid electrolyte-soaked separator
between two stainless steel plate electrodes could be calculated using
the following equation [18]:
d
σ¼
R�S
Where σ is the ionic conductivity, R is the bulk resistance obtained from
Journal of Power Sources 461 (2020) 228123
the Nyquist plots, d and S represent the thickness and the effective area
of relevant fibrous membranes, respectively.
CR2032 coin cells were assembled by sandwiching relevant mem­
branes between the LiFePO4 cathode and the Li metal anode in an argon-
filled glove box. The first-charge-discharged test of cells was performed
between 2.0 and 3.6 V under a current density of 0.2 C at room tem­
perature. The cycle performance was conducted in cells with a voltage
range of 2.0 – 3.6 V under a rate of 0.2 C for 50 cycles at room tem­
perature. The C-rate capability was measured at 45 � C over a voltage
range of 2.0 – 3.6 V under different charge current density of 0.2, 0.5,
1.0, 2.0 and 0.2 C, respectively.
(1)
3. Results and discussions
3.1. Morphology and structure of bicomponent nonwoven
Fig. 2 demonstrated the microscopic morphology and corresponding
fibers diameter distribution of the as-prepared membranes. It can be
(2) found from the SEM images that the electrospun nonwoven had the
prominent pore structure and 3D network structure, which facilitated
the electrolyte uptake and provided an abundant channel for the ion
migration in LIBs [28]. The side-by-side PVDF-HFP/PI fibers exhibited
the obvious parallel structure and uniform fiber diameter distribution
(Fig. 2d), while the PVDF-HFP, PI and PVDF-HFP þ PI fibers were
smooth single fibers, indicating the effective preparation of side-by-side
bicomponent fibers. Moreover, the parallel structure of PVDF-HFP/PI
fiber was intuitively distinguished by the fluorescence microscope
(Fig. 1), and the side-by-side bicomponent fibers were composed of the
PVDF-HFP fiber showing green fluorescence and the PI fiber with red
fluorescence.
The chemical composition of relevant nonwovens was characterized,
as presented in Fig. 3. The characteristic IR absorption peaks (Fig. 3a) of
PVDF-HFP/PI and PVDF-HFP þ PI nonwovens appearing at 735, 1375,
1720 and 1770 cm 1 were attributed to the amide ring structure of PI
and 1174 cm 1 belonging to the vibration of CF3 group in PVDF-HFP [9,
17], confirming the successful fabrication of bicomponent fibers. In
addition, the XRD data (Fig. 3b) showed that the dispersion peak of
electrospun PI nonwoven appeared at 2θ ¼ 20 � , illustrating an amor­
phous structure [29]. And the PVDF-HFP fibers possessed a relatively
high crystallinity with two distinct sharp diffraction peaks at 18.3 and
(3) 20.3 � [30]. For the bicomponent membranes, the crystal diffraction
peaks of PVDF-HFP were distributed on the PI dispersion peak, which
also suggested that the PVDF-HFP/PI and PVDF-HFP þ PI nonwovens
4
M. Cai et al. Journal of Power Sources 461 (2020) 228123

Fig. 4. SEM images of PVDF-HFP þ PI (a) and PVDF-HFP/PI (b) after thermal cross-linking treatment, DSC curve of PVDF-HFP membrane (c), stress-strain curves of
PI, PVDF-HFP þ PI and PVDF-HFP/PI electrospun membranes before (d) and after (e) thermal cross-linking treatment.

contained both polymers.

Table 1
Physical properties of the separators.
3.2. Mechanical properties and wettability analysis
Sample PVDF-HFP þ PI PVDF-HFP/PI Celgard2320
(T) (T)
Excellent mechanical strength was conducive to improve the service
Thickness (μm) 24 23 20 life and safety of LIBs. However, the strength of electrospun nonwoven
Porosity (%) 80.1 85.9 46.1
was generally low, and the tensile strength of the single-component PI
Electrolyte uptake (%) 422.7 483.5 80.3
Ionic conductivity (S/ 0.68 � 10 3
1.78 � 10 3
0.16 � 10 3 membrane was only 2.55 MPa (Fig. 4d). In order to enhance the strength
cm) and avoid destroying the pore structure of nonwovens, the bicomponent
Average pore size (μm) 1.361 1.779 0.05 membranes were treated by thermal cross-linking method [11,31].
Through controlling the temperature and time of the cross-linking
treatment, the PVDF-HFP with a low melting point was partially mel­
ted and consolidated to strengthen the bonding between fibers, while
the high temperature resistant PI acted as the skeleton material to

Fig. 5. The wettability (a) and contact angles (b) of the liquid electrolyte on the relevant membranes.

5
M. Cai et al.
Fig. 6. The TGA curves (a), corresponding DTG curves (b) and thermal
dimensional stability (c) of relevant membranes.
maintain the morphology of the fibers, as shown in Fig. 4a and b. It was
worth mentioning that the melting point of PVDF-HFP was determined
to be at about 140 � C by DSC (Fig. 4c), thus the temperature of thermal
cross-linking treatment was chosen at 145 � C. As expected, the me­
chanical properties of the cross-electrospun PVDF-HFP þ PI and the
side-by-side PVDF-HFP/PI nonwovens (Fig. 4d and e) were effectively
ameliorated, and the reinforcing effect of the side-by-side nonwoven
was better, reaching 9.76 MPa. Besides, compared with the PVDF-HFP
þ PI(T) membrane, the binding points distribution of PVDF-HFP/PI(T)
6
Journal of Power Sources 461 (2020) 228123
nonwoven were relatively uniform, and the porosity and microstruc­
ture of the fibers were better maintained (Fig. 4a and b). Specifically, the
porosity of the PVDF-HFP/PI(T) nonwoven was about 85.9 %, which
was higher than that of PVDF-HFP þ PI(T) (80.1 %), leading to an
excellent electrolyte uptake (483.5 %), as detailed in Table 1. Moreover,
it was found that the holes of electrospun nanofiber nonwovens were not
through holes, but through overlapping holes [32]. As the electrospun
nanofiber nonwovens were multilayer structures formed by random
stacking of fibers, the pore size of electrospun nanofiber nonwovens may
be micron-scaled in the surface layer, sub-micron scaled in the second or
third layer, nano-scaled in the fourth or fifth layer, and even less in the
deeper inner layer. Therefore, even if the average pore size of
PVDF-HFP/PI(T) nonwovens reached the micron level, as shown in
Table 1, the electrospun nanofiber separator still worked well in LIBs. In
other words, the uniform 3D cross-linked structure of the PVDF-HFP/PI
(T) side-by-side fibrous nonwoven was both advantageous for enhancing
mechanical properties and maintaining high electrolyte uptake.
Fig. 5 presented the wettability and contact angle of the relevant
membranes with liquid electrolyte. It can be clearly seen that the elec­
trolyte on the surface of PVDF-HFP/PI(T) and PVDF-HFP þ PI(T) non­
wovens spread and wetted rapidly, while the electrolyte on the
Celgard2320 separator appeared as water droplets and remained sub­
stantially intact after 1 min (Fig. 5a). Meanwhile, the contact angle of
PVDF-HFP/PI(T) and PVDF-HFP þ PI(T) nonwovens with the electrolyte
was close to 0 � (Fig. 5b), and the contact angle of Celgard2320 mem­
brane was about 42 � 3 � .These results revealed that the PVDF-HFP/PI
(T) membrane possessed both favorable wettability and affinity to the
electrolyte. It was mainly due to the high porosity of the PVDF-HFP/PI
(T) nonwovens and good affinity between PVDF-HFP, PI and electrolyte,
which was beneficial to the improve the ionic conductivity and elec­
trochemical performance.
3.3. Thermal stability characterization
The thermal stability of the nonwoven using as a separator is also one
of the important factors determining the safety of batteries, and the TGA
and corresponding DTG were performed to investigate the thermal
properties of the as-prepared membrane. As shown in Fig. 6a and b, the
weightlessness process of PVDF-HFP/PI nonwoven roughly displayed
two stages: initially, the PI polymer formed from the remaining PAA in
the purchased PI solution before 200 � C, and a followed pyrolysis stage
of the polymer macromolecule started at about 565 � C. Additionally, the
TGA curve of the PVDF-HFP/PI side-by-side nonwoven was very close to
that of PI fibers, emerging excellent thermal property. It may be due to
the close contact of PVDF-HFP and PI in the side-by-side fiber, leading to
a two-phase mixing action under elevated temperatures. Fig. 6c illus­
trated the thermal dimensional stability of the relevant membrane after
heat treatment at 150 and 200 � C for 30 min. It was found that the
Celgard2320 membrane shrunk rapidly to about 50 % at 150 � C, and
completely melted and contracted at 200 � C. Similarly, although the
PVDF-HFP nonwoven owned good extensibility, their application in
lithium battery separator was greatly limited owing to thermal
shrinkage. It was well known that PI possessed excellent heat resistance
[26], thus PI and the bicomponent fibrous nonwovens with the PI as
skeleton showed good thermal dimensional stability and the area
shrinkage caused by heat treatment could be ignored. Moreover, the
fibrous nonwoven was subjected to a combustion test, as illustrated in
Fig. 7. After the flame was withdrawn, the Celgard2320 and PVDF-HFP
membrane continued to burn, accompanying with an open flame, and
PVDF-HFP/PI(T) membrane rapidly extinguished. As a result, the 3D
cross-linked side-by-side PVDF-HFP/PI(T) nonwoven owned
outstanding thermal stability and flame-retardant property, providing
the reliable high temperature security for LIBs.
M. Cai et al. Journal of Power Sources 461 (2020) 228123

Fig. 7. The combustion tests of the Celgard2320, PVDF-HFP and PVDF-HFP/PI(T) membranes, respectively.

Fig. 8. Electrochemical stability windows (a), AC impedance spectra (b), Nyquist plots (c) of relevant membranes measured at room temperature. (d) Illustration
showing lithium ion transmission of the PVDF-HFP/PI(T) separator.

7
M. Cai et al.
Fig. 9. (a) The schematic of the battery assembling, first charge/discharge curves (b) and cycling performance (c) of the Celgard2320, PVDF-HFP þ PI(T) and PVDF-
HFP/PI(T) separator at room temperature, (d) rate capability of PVDF-HFP/PI(T) separator at 45 � C.
3.4. Electrochemical performance evaluation
The electrochemical stability window of the PVDF-HFP/PI(T)
nonwoven separator was evaluated by Linear sweep voltammetry
measurement (vs. Liþ/Li) at a scan rate of 5 mV s 1, as depicted in
Fig. 8a. It can be obtained that the PVDF-HFP/PI(T) nonwoven showed a
wider electrochemical stability window than the Celgard2320 separator,
revealing that the PVDF-HFP/PI(T) owned better anodic stability with
electrolyte. Moreover, the current of the PVDF-HFP þ PI(T) separator
sharply increased with a polarization reaction at 4.89 V vs. Liþ/Li, while
the PVDF-HFP/PI(T) separator kept stable below 4.94 V vs. Liþ/Li,
which was related to the high porosity and superior electrolyte retention
of PVDF-HFP/PI(T) nonwoven [33]. Fig. 8b presented the AC impedance
of the separators performed on two symmetric stainless-steel electrode
cells, and the intercept of the curve and the x-axis was the bulk resis­
tance (R) of the polymer electrolyte. Benefiting from the high porosity
and excellent liquid electrolyte uptake, the ionic conductivity of
PVDF-HFP/PI(T) separator was 1.78 � 10 3 S/cm, which was higher
than that of PVDF-HFP þ PI(T) separator (0.68 � 10 3 S/cm) and Cel­
gard2320 separator (0.16 � 10 3 S/cm), as summarized in Table 1,
showing the outstanding ion transport property of PVDF-HFP/PI(T)
separator.
Furthermore, the compatibility of liquid electrolyte-soaked PVDF-
HFP/PI(T) separator with lithium metal was studied by measuring the
EIS spectra in the Li/liquid electrolyte-soaked separator/Li cells, as
shown in Fig. 8c. The diameter of the semicircle in the Nyquist plots
denoted the overall interfacial resistance, which consisted of contact
resistance (Rs), that corresponding to the contact membrane resistance,
and charge transfer resistance (Rct) related to lithium ion interfacial
transfer between electrodes and electrolyte interface [11,34]. The Rct
values of Li/liquid electrolyte-soaked separator/Li cells were confirmed
by fitting as follows: PVDF-HFP/PI(T) < PVDF-HFP þ PI(T) < Cel­
gard2320 [11], confirming that the transportation of the lithium ion
between electrodes and electrolyte interface was more efficiently when
the cell was assembled with PVDF-HFP/PI(T) separator. The study
showed that the interfacial resistance largely depended on the
8
Journal of Power Sources 461 (2020) 228123
compatibility of surfaces between separator and electrode [35–37]. The
lowest charge transfer resistance of PVDF-HFP/PI(T) separator could be
explained by the fact that the high porosity, uniform interconnected
pore structure and the component advantages of PVDF-HFP/PI(T)
nonwoven facilitated the compatibility between the lithium electrode
and the PVDF-HFP/PI(T) separator, which was advantageous to the
good interfacial transfer process of lithium ion. Besides, we qualitatively
modelled the transmission process of lithium ions across side-by-side
PVDF-HFP/PI(T) fibrous separator by simulating the infiltration of
electrolyte in the membrane using GeoDict 3D software [38]. Based on
the SEM images, considering the fiber morphology and stacking density
of PVDF-HFP/PI(T) nonwoven, a 3D geometric cubic fibrous separator
was established. Subsequently, the density, dynamic viscosity, ion
conductivity and lithium ion diffusion coefficient of the electrolyte
(Table S1) were taken into account in the simulation to obtain the
migration process of lithium ion across the separator [39,40]. The
simulation result was shown in Fig. 8d, in which blue indicated a slow
transmission rate and the red velocity meant fast. It was apparent that
the transportation of lithium ion in the PVDF-HFP/PI(T) separator was
relatively uniform, which illustrated that the pore structure in the
cross-linked PVDF-HFP/PI(T) side-by-side fibrous nonwovens was
beneficial to the homogeneous transmission of lithium ion [2].
The battery performances of the sample membranes, including the
first charge-discharge capacity performance, cycling tests and rate
capability, were evaluated by assembling the Li/separator/LiFePO4 coin
cell, as illustrated in Fig. 9a. It was found that all the coin batteries using
PVDF-HFP/PI(T), PVDF-HFP þ PI(T) and Celgard2320 as separators
showed the stable charge-discharge platform between 2.0 and 3.6 V
under a current density of 0.2 C (Fig. 9b), which satisfied the demands of
LIBs. Meaningfully, the first discharge capacity and coulombic efficiency
of PVDF-HFP/PI (T) separator were the largest among the three
assembled batteries, which are 120.41 mAh g 1 and 99.36 %, respec­
tively. From the cycling curves of the relevant separator in Fig. 9c, we
obtained that the discharge capacity of the battery employing the PVDF-
HFP/PI(T) nonwoven as separator kept at around 118.15 mAh g 1 after
the 50 cycles with a capacity retention of 98.13 %, while that of the
M. Cai et al.
PVDF-HFP þ PI(T) and Celgard2320 separator decreased to 96.09 and
94.9 1%, respectively. Furthermore, for the sake of determining the
potential of PVDF-HFP/PI(T) separator in the high temperature safety
and performance stability of LIBs, the rate capability of Li/PVDF-HFP/PI
(T)/LiFePO4 coin cell was evaluated at 45 � C. As shown in Fig. 9d, the
coin cell using PVDF-HFP/PI(T) separator at 45 � C showed the discharge
capacity about 117.76 mAh g 1 at 0.2 C, 112.40 mAh g 1 at 0.5 C, 98.31
mAh g 1 at 1.0 C and 80.04 mAh g 1 at 2.0 C, respectively. It was found
that the PVDF-HFP/PI(T) separator exhibited good discharge capacity
under different discharge C-rate at 45 � C [41]. These favorable battery
performances of Li/PVDF-HFP/PI(T)/LiFePO4 were attributed to the
high porosity, good ionic conductivity, low interfacial resistance and
fine thermal stability of the PVDF-HFP/PI(T) nonwoven. In addition, the
homogeneous transmission of lithium ion in the cross-linked
PVDF-HFP/PI(T) side-by-side nonwoven was also beneficial to the
good performance of the battery.
4. Conclusion
In this work, the PVDF-HFP/PI side-by-side bicomponent fibrous
membrane with 3D cross-linked structure was successfully prepared by
electrospinning method and subsequent thermal cross-linking treat­
ment. It was demonstrated that by the introduction of the bonding be­
tween the fibers, the mechanical strength of PVDF-HFP/PI nonwovens
was effectively improved. Importantly, the post-treated nonwoven,
PVDF-HFP/PI(T), still exhibited high porosity of 85.9 %. The results
showed that the PVDF-HFP/PI(T) composite separator emerged excel­
lent performance, including excellent electrolyte uptake, ionic conduc­
tivity, wide electrochemical stability window, good interface structure,
thermal dimensional stability and self-extinguishment. Furthermore, the
3D simulation confirmed that the transportation of lithium ion in the
PVDF-HFP/PI(T) separator was relatively uniform by simulating the
infiltration of electrolyte in the membrane, which was beneficial to the
homogeneous transmission of lithium ion. As assembled into the battery
test, the first charge-discharge capacity and cycle performance of the
side-by-side PVDF-HFP/PI(T) separator were evidently superior to those
of the Celgard2320 separator and cross-electrospun PVDF-HFP þ PI(T)
separator. Furthermore, the coin cell using the PVDF-HFP/PI(T) sepa­
rator exhibited good discharge capacity under different discharge C-rate
at 45 � C, showing its potential for the high-temperature safety of LIBs.
To sum up, the PVDF-HFP/PI(T) membrane has a prospect for applica­
tion in the field of LIBs separators, which also provides a strategy for the
design of new electrospun separator with improved performance.
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.
CRediT authorship contribution statement
Ming Cai: Conceptualization, Methodology, Data curation. Ding
Yuan: Conceptualization, Methodology, Data curation, Writing - orig­
inal draft, Writing - review & editing. Xiao Zhang: Software. Yi Pu:
Software. Xiaofang Liu: Resources. Hongwei He: Formal analysis.
Lixue Zhang: Formal analysis. Xin Ning: Conceptualization, Resources.
Acknowledgements
The financial support of the Natural Science Foundation of China
(Grant No. 21802079) and Postdoctoral Science Foundation of China
(Grant No.2018M642605) are appreciated.
9
Journal of Power Sources 461 (2020) 228123
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2020.228123.
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