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Eco-friendly polyvinyl alcohol/cellulose

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nanofiber–Li+ composite separator for high-

Cite this: RSC Adv., 2016, 6, 97912
performance lithium-ion batteries
Chuanting Liu,a Ziqiang Shao,*b Jianquan Wang,b Chengyi Luc and Zhenhua Wangc

A novel eco-friendly polyvinyl alcohol/cellulose nanofiber–Li+ (PVA/CNF–Li) composite separator was

Received 20th July 2016
Accepted 2nd September 2016
DOI: 10.1039/c6ra18471e
www.rsc.org/advances
prepared for lithium-ion batteries. In this membrane by a non-solvent induced phase separation (NIPS)
wet-process, CNF–Li originating from wood pulp was successfully prepared and characterized by FT-IR
and TEM. The composite separators showed excellent porosity of over 60%, and better ionic
conductivity (
1.1 mS cm1) as well as remarkable electrolyte uptake approaching 2.3. CNF–Li combined
the excellent properties of both nanofibers and ion-conductive polymers such as CMC–Li. The
introduction of CNF–Li in the separator increased the thermal dimensional stability and mechanical
performance. Simultaneously, CNF–Li as a constituent in the membrane increased the contents of Li+,
opening a way for Li+ transportation to improve batteries' Li+ diffusion efficiency and specific capacity.
The battery with a 2 wt% CNF–Li separator retained 93% of the initial reversible capacity after 50 cycles,
which was much higher than that of the commercial polypropylene (PP) separator with a value of 80%.
The PVA/CNF–Li composite membrane produced via a relatively low cost and eco-friendly method can
serve as a potential alternative of commercial PP separators applied in high-performance lithium-ion
batteries.

electrolytes (due to hydrophobicity and low surface energies of

1. Introduction
Rechargeable power sources in a clean and smart energy envi-
ronment with reliable electrochemical properties, robust
safeties and from sustainable sources are greatly demanded by
the tremendous progress of electric vehicles and energy storage
systems.1,2 Among different kinds of energy storage systems,
lithium-ion batteries are surely an important trend, specically
in portable electronics.3–7 As one of the major battery compo-
nents, a separator acts as a barrier between the two electrodes,
preserves the liquid electrolyte and provides microporous
channels to allow ions to ow through, which is critical to
batteries' safety and performance and should not be
underestimated.8–13
Nowadays, polyolen polymers such as PE and PP are the
most commercially available separators in the consumer
market owing to their chemical stability and uniformity in pore
size distribution. However, PE and PP separators have inferior
thermal stability and are not well compatible with some
a
School of Material Science and Engineering, Beijing Institute of Technology, Beijing
100081, China
b
Beijing Engineering Research Centre of Cellulose and Its Derivatives, Beijing 100081,
China. E-mail: shaoziqiang@263.net
c
Beijing Key Laboratory for Chemical Power Source and Green Catalysis, School of
Chemical Engineering and Environment, Beijing Institute of Technology, Beijing
100081, China
the polyolen), thus restricting their application in high
performance batteries.
Despite such popularity, their inferior thermal stability and
limited compatible with some electrolytes (due to hydropho-
bicity and low surface energies of the polyolen) restricted the
application in high performance batteries.14–19 To overcome the
drawbacks of polyolen-based separators, several approaches
have been explored, such as polymer coatings,20 incorporation
of inorganic nano-particles,21–23 electro-spinning nonwoven
separators.24–27 However, separators fabrication usually involve
toxic and contaminated solvents28 and based on exhausted
fossil oil that is stubbornly at odds with the achieve green, low-
carbon and sustainable development, based on that, renewable
polymers such as cellulose, PVA as an alternative to PP and
PE28–30 have attracted a lot of attention. Cellulose's application
to energy storage systems25,31,32 has been extensively investi-
gated for its high dielectric constant, good chemical stability,
good hydrophilicity, superior thermal stability33–36 and natural
abundance.28 Many efforts have been made to develop high-
performance separators from low cost, renewable cellu-
lose.25,28,37 It is also published that effective ion-conductive
polymer like CMC–Li with groups of –COO–Li can increase
the contents of freely moving lithium ions in lithium-ion
batteries and shorten the diffusion pathway to the cathode
particle surface.49–51 Inspired by this, CNFs prepared by TEMPO-
mediated system, almost all of the C6-primary hydroxyl groups

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exposed on the crystalline cellulose microbrils are converted to
–COO–Na, –COO–Li can get through ion-exchange method.
Besides, cellulose nanober (CNF) is one of special forms
cellulose presented big aspect ratio, high elastic modulus,41 low
density, high crystallinity, small thermal expansion coefficient42
etc., attracting great attention in energy storage area as a rein-
forcing agent43,44 and substrate.45 Mechanically robust and
thermal shrinkage of the separator are essential factor to eval-
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uate safety characteristics and battery performance of the
lithium-ion battery.3,46
Several researches have justly reported that CNF's mass
production was successfully realized,47–49 which solved the
difficulties of sampling. CNF–Li getting from ion-exchange
method may possess both the performances of CNFs and ion-
conductive polymer like CMC–Li for same group –COO–Li is
gotten through ion-exchange method, which possess both
performances of CNF and CMC–Li for same group of –COO–Li.
CNF–Li probably could do favor to the mechanical, thermal
properties like CNF and simultaneously increase the contents of
freely moving lithium ions in lithium-ion batteries and shorten
the diffusion pathway to the cathode particle surface similar to
CMC–Li.50 Polyvinyl alcohol (PVA) with excellent thermal,
mechanical, chemical stabilities and good lm-forming prop-
erty has also been used as battery components.51–53 Herein,
a new class of polyvinyl alcohol/cellulose nanober–Li+ (PVA/
CNF–Li) composite lithium-ion battery separator is reported for
the rst time. Here the critical substrate PVA performs the
crucial property, i.e., thermal shutdown ability. The character-
istics of the composite separator are evaluated in terms of
morphology, structure, thermal shrinkage, electrolyte wetta-
bility, ionic conductivity and the electrochemical performances.
Another motivation of this work sheds light on an ideal
substitute of synthetic polymer derived from fossil oil by
Fig. 1 (a) The mechanism of preparation CNF–Li and (b–d) the fabrication method of separator.
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renewable polymer as clean energy material owing to its versa-
tile diversity and easy process ability.
2. Experimental
2.1. Materials
Poly(vinyl alcohol) (PVA) was supplied by Shanghai Yuanli
Chemical Co. (Shanghai, China) with hydrolysis of 97% and
molecular weight of 72 000 g mol1. Dried sowood breached
eucalyptus pulp from South China University of Technology
(SCUT), ethanol (100%), TEMPO (2,2,6,6-tetramethylpiperidine-
1-oxyl) (Aladdin Chemistry Co. Ltd), sodium hypochlorite,
sodium bromide and lithium hydroxide (Sinopharm Chemical
Reagent Beijing Co. Ltd), hydrochloric acid (36–38 wt%) (Sino-
pharm Chemical Reagent Beijing Co. Ltd). All solvents and
chemicals were used as received.
2.2. Preparation for cellulose nanober–Li+ (CNF–Li+)
2.2.1. TEMPO-mediated oxidation. Cellulose bers (15 g)
was suspended in water (3000 mL) containing TEMPO (0.5 g)
and sodium bromide (5 g). The oxidation reaction was started
by adding 100 g NaClO solution. The pH of the reaction main-
tained at 10. The oxidized cellulose was then washed, sonicated
and centrifuged to obtain cellulose nanober–Na (CNF–Na)
with solid content of 1% according to the methodology reported
by Isogai (Fig. 1).54
2.2.2. Preparation for cellulose nanober–Li+ (CNF–Li+). To
prepare the cellulose nanober (CNF–H) with protonated
carboxyl groups, 1 M HCl was added to a 0.1% CNF–Na/water
slurry to adjust the pH value to 2, and the slurry was stirred
for 12 h. The CNF–H was washed with 0.50 M HCl and then with
water, using ltration, until the pH of the CNF–H/water slurry
was about 4. A certain amount of a 7 wt% aqueous solution of
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lithium hydroxide was then added to the aqueous CNF–H/water
slurry with a rough estimation of 0.07 w/v% to keep the pH value
to 10. The slurry was stirred at room temperature for 12 h or so.
Then, the slurry was dialyzed for 5 days until its pH reached 7.
Then 2 mg mL1 CNF–Li slurry/water was sonicated for 15 min
at power of 300 W in an ice bath. Cellulose nanobers disper-
sion was centrifuged at 10 000 rpm for 10 min to remove the
unbrilated cellulose. The cellulose nanober (CNF–Li)
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dispersion was stored at 4  C with solid content of 1.64% before
use.
Separators were prepared through the non-solvent induced
phase separation (NIPS) wet-process method.46 PVA powder was
dissolved in deionized water at 90  C using mechanical stirring
in microwave oven with power of 200 W for about 25 minutes to
make PVA aqueous solution (10 wt%). Before the lm building,
the solution should be cooled down to room temperature and
remove entrapped air bubbles. Homogenous PVA solution was
casted onto a glass plate at room temperature, using a casting
knife with 150 mm thickness and 2.5 cm s1 velocity, and
immediately immersed in a coagulation bath containing 100%
ethanol at room temperature for 36 h. The separator was then
removed from ethanol and dried at room temperature for 24 h
before further characterization. 1 wt%, 2 wt% and 3 wt%
cellulose nanober–Li of (CNF–Li)/polyvinyl alcohol (PVA)
composite separator and pure PVA separator (later with PVA-
1%, PVA-2%, PVA-3% and PVA in the paper) were prepared.
Meanwhile, a commercialized PP separator was also investi-
gated for comparison in this study.
3. Results
3.1. Characterization of cellulose nanober–Li+ (CNF–Li)
In the TEM image of CNF–Li sample (Fig. 2a), nanobers are
long bers with, diameter of 4–8 nm and length of 800–1000 nm
(aspect ratio $ 100) and they are homogeneously dispersed
owing to TEMPO-mediated oxidation and the uniform distri-
bution of Li+ on the surface. The FT-IR spectra of the initial
product CNF–Na, the intermediate product CNF–H and the
resultant CNF–Li are shown in Fig. 2b. –OH stretching at 3400–
3300 cm1 can be found in all of these spectra and the CNF–H
spectrum is considerably different from those of CNF–Na and
Fig. 2 (a) TEM image of CNF–Li sample and (b) FT-IR spectra of CNF–Na, CNF–H, CNF–Li.
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CNF–Li, which demonstrated that the molecular structure of
CNF–H is signicantly different from the others. The peaks of
CNF–H and CNF–Li spectra are very different at 1720, 1638 and
1590 cm1, respectively. It can be explained –C]O and –C–O
bonds coupled with the same carbon atom are homogenized
aer the carboxylic acid protons replaced by Li ions. The bond
length of homogenized carbon oxygen was between double
bond –C]O and single –C–O because stretching vibration of
two homogenized carbon oxygen was strong coupled, and there
are two absorption bands at 1720 and 1638 cm1, which
conrmed the formation of CNF–H. As an important interme-
diate product from CNF–Na to CNF–Li, CNF–H can help judge
the resulting product CNF–Li. In addition to the characteristic
peaks of the common structure of cellulose nanobers either,
there were more obvious difference between two kinds of car-
boxymethyl cellulose salt at 565 cm1, therefore CNF–Li was
successfully synthesized.
3.2. Morphology and mechanical properties of the
composite separator
The surface and cross-section SEM images of the PVA, PVA-1%
and PVA-2% separators are shown in Fig. 3a, b, c showed
surface SEM images of PVA, PVA-1%, PVA-2% separately;
Fig. 3d, e, f demonstrated cross-sectional SEM images of the
PVA, PVA-1% and PVA-2% respectively. The surface of separator
is highly homogeneous and smooth without obvious defects.
Moreover, the separator possessed highly interconnected
sponge-like porous structure, which was formed during the
solvent/non-solvent exchange process in the coagulation bath.53
Separators thickness was about 25 mm. The pore distribution
was tested through mercury intrusion method. Fig. 3g, h, i
presented the pore size distribution of the PVA, PVA-1% and
PVA-2% respectively. The pore was very uniform and the average
pore size were 0.17 mm, 0.32 mm, 0.26 mm respectively. The data
of porosity was measured by immersing the separator into n-
butanol for 2 h and then calculated according to an equa-
tion,25,55 listed in Table 1. It is observed that the porosity of PVA-
based composite separators' was above 60%, much higher than
that of the PP separator (about 40%). In the NIPS process for
separator fabrication, the PVA based separators with symmetric
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Fig. 3 The SEM images (a–f) and pore size distribution (g–i) of the PVA based separators.
structure were formed because of the trade between thermo-
dynamic enhancement and kinetic hindrance,25,55 while the
kinetic hindrance was dominated in this process.53 The well
dened three-dimensional porous separator based on PVA can
be obtained by a simple phase separation process without pore
forming additives. As we can see the data in the Table 1, the
introduction of CNF–Li had no side-effects to the porosity of
obtained separators. It can be speculated that higher porosity
will contain more electrolyte and result in more effective ion-
conducting during cycling.53
Lithium ion battery separator should be mechanically robust
enough to withstand the high tension aer casual collisions
and prevent internal short-circuits caused by the rough elec-
trode surface, debris and growth of lithium dendrite.3,46 The
stress–strain curves of separators were depicted in Fig. 4 and
Table 1. It was clearly demonstrated that the import of the
certain amount of CNF–Li had positive effects on the strength
for the PVA based separators. The tensile strength of PVA, PVA-
1%, PVA-2% was 13.0 MPa, 15.0 MPa and 18.0 MPa respectively,
but that of PVA-3% decreased to 6.5 MPa, probably resulted
from the serious agglomeration of CNF–Li under high viscosity
because small particles were found by snake eyes on the surface
of the wet membrane during processing. Also, the tensile
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strengths of PVA based separators in this study are a little better
than that of commercial PP separator (12.0 MPa).25 Studies43,44
have found that CNF is good strengthening agent in composite
materials. Besides, –COO on the CNF–Li hindered the aggre-
gation of nanobers. A large number of hydroxyl groups on both
components formed hydrogen bonds in homogeneous solution,
also contributing to establishing a well-mixed system. CNF–Li
played a positive role in the mechanical performance of the
composite separators.
3.3. Electrolyte wettability
The wettability of separators was evaluated by liquid electrolyte
contact angle as shown in Fig. 5. Wetting test was carried out by
dropping a drop of electrolyte onto the surface of each separator
and measuring the contact angle as soon as liquid electrolyte
touched surface.
As illustrated in Fig. 5a, b, c, d presented liquid electrolyte
contact angles of PP, PVA, PVA-1% and PVA-2% respectively, the
contact angle of PVA based separators was only about 8.5  C
compared with 42.5  C of the PP separator, which was much
lower than that of the PP separator. While the amount of the
CNF–Li in PVA based separators didn't affect wettability much
because their contact angles were nearly the same. To further
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Table 1 Physical properties of separators
Separator PP PVA PVA-1% PVA-2% PVA-3%
Thickness (mm) 25.0 23.0 23.0 25.0 25.0
Porosity (%) 41.0 64.7 65.7 66.9 67.1
Tensile strength (MPa) 12.0 13.0 15.0 18.0 6.5
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investigate the electrolyte performance of the separators, the
electrolyte uptake was studied according to the electrolyte
uptake test.3,19,53 The electrolyte uptake of PP, PVA, PVA-1%,
PVA-2% was 1.17, 2.22, 2.30 and 2.34 respectively. The differ-
ence in electrolyte wettability conrmed that the obtained PVA
based separators was more electrolyte-philic, which led to better
transportation of Li+ ions through the separator.19 The excellent
electrolyte wettability of PVA based separator is mainly attrib-
uted to the following two reasons. One is the strong affinity of
PVA and CNF–Li chains toward electrolyte solvent mole-
cules.29,53 The other is the capillary force due to the inter-
connected sponge-like porous structure in PVA based separator.
Considering the superior electrolyte wettability, the PVA based
separator is expected to endow the lithium-ion batteries with
higher ionic conductivity and better discharge performance.11
3.4. Thermal stability
Thermal shrinkage of the separator was another essential factor
to evaluate safety characteristics and battery performance of the
lithium-ion battery.3,46 Fig. 6a showed photographic images of
separators before and aer exposure to 160  C for 1 h. It can be
seen that the PVA based separators exhibits superior thermal
stability with almost no dimensional change aer the heat
treatment, as compared to PP separator showing thermal
shrinkage of about 51%. The excellent thermal resistance of
PVA material was also reported because its meltdown peak was
about 275–280  C, much higher than the common operating
temperature of batteries.26 The thermal shrinkage of the sepa-
rators was further compared by measuring their dimensional
changes subjected to heat treatment every 20  C from 120  C to
240  C for 1.0 h. As shown in Fig. 6b, the difference in the
thermal shrinkage between PVA based separator and PP sepa-
rator becomes more pronounced as the temperature was
Fig. 4 Stress–strain curve of separators.
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increased. Since PP's melting temperature was about 200  C, the
PP separator continued to shrink with increasing temperature
of dimensional shrinkage ratios of about 81% and 99%,
respectively, when the temperature was raised to 160  C and 200

C. By comparison, the dimensional change of PVA based
separator was very small over a wide range of temperature. For
example, the shrinkage ratios of PVA separator are only 1% and
3% when temperature was raised to 160  C and 200  C,
respectively. Besides, the more CNF–Li added, the smaller
shrinkage we got. For example, the shrinkage of PVA-2%, PVA-
1% and PVA at 240  C was 62%, 64%, 70%, respectively. The
results might be attributed to the separator materials and the
preparation methods. The melting temperature of PVA was
about 270  C and the cellulose nanobers' good thermal resis-
tance was also reported47, both of which contributed to good
dimensional stability. Simultaneously, the separator from wet
phase separation method possessed better thermal stability
compared to that from stretching process. PP separator was
more likely to lose dimensional stability than PVA base sepa-
rator, so it was easier for PP separator to lose dimensional
stability than PVA based separator via the NIPS wet-process53 In
addition, the introduction of CNF–Li improved the thermal
stability of PVA separator to some extent for nanobers' small
thermal expansion coefficient41 and metal-ion exchange.45 Good
dimensional stability of CNF–Li/PVA composite membrane
could effectively prevent internal electrical short circuit at
elevated temperature when the battery is at high charged/
discharged rates.
3.5. Electrochemical performance of separators
Electrochemical stability of the electrolytes within the operation
voltage of a battery system is important for practical battery
applications. The electrochemical stability window of the
separators was evaluated by linear sweep voltammetry as shown
in Fig. 7a. The membranes were sandwiched between one
lithium foil sheet and one stainless steel sheet for the
measurement. When the voltage was higher than 4.3 V,
a considerable increase in current ow was found for the PP
Fig. 5 The liquid electrolyte contact angles of separators.
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Fig. 6 (a) Photographic images for PP, PVA, PVA-1%, PVA-2% before (a–d) and after (e–h) exposure to 160  C for 1.0 h, respectively. (b) Thermal
shrinkage properties of separators.
separator, while, PVA, PVA-1% and PVA-2% showed higher
decomposition voltage of 4.7 V, 5 V, 5.2 V. Besides, a distinct
improvement was found with increasing amount of CNF–Li,
further proving the inertness of PVA/CNF–Li separator. This
result demonstrated the PVA based separator was stable enough
to endure the operating voltage of the battery system.
Based on the comparisons of electrolyte wettability and
thermal stability between PVA based separators and PP sepa-
rator, the electrochemical impedance spectra of the separators
were illustrated as Nyquist plots of separators in symmetric
lithium coin cells in Fig. 7b. Impedance spectroscopy was used
to characterize the ionic conductance for separators impreg-
nated with the liquid electrolytes and sandwiched between two
lithium foils for the measurement. The impedance spectra
depicted a smaller semicircle for PVA based separators than PP
separator. The semicircle in the impedance spectra usually
related to the interfacial resistance of a separator was reported,
lower interfacial resistance usually indicated better interfacial
compatibility with lithium electrodes46,56 At the same time,
Fig. 7b showed the larger amount of CNF–Li in composite
separator led to better interfacial compatibility.
In addition, the stainless steel/separator/stainless steel cell's
AC spectra were typically inclined straight line for stainless steel
blocking electrodes. The line inclined towards the Z0 axis
demonstrated the electrode/electrolyte double layer capacitance
behavior.47 Thus, the bulk resistance of the separator can be
Fig. 7 (a) Linear sweep voltammetry of the separators. (b) Nyquist plots of separators in symmetric lithium coin cells.
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acquired from the high-frequency intercept of the Nyquist plot
on the Z0 axis. The bulk resistances of PVA, PVA-1% and PVA-2%
separator were about 3.4 U, slightly lower than the 4.4 U value of
PP separator. PVA based separators exhibits better ionic
conductivity with 1.1 mS cm1 compared to 0.55 mS cm1 for
PP separator at room temperature.
Practicality of separators in battery cell was evaluated by
using a lithium metal anode and a LiCoO2 cathode impregnated
with the liquid electrolytes of 1 M LiPF6 in the EC : DEC : EMC
¼ 1 : 1 : 1 solvents charged over a voltage range of 2.8–4.2 V at
a constant current density of 0.2C (0.42 mA cm2) and dis-
charged at different current densities ranging from 0.2C (0.42
mA cm2) to 4.0C (8.4 mA cm2).
Cycling stability of the cells with separators at room
temperature under 0.2C was presented in Fig. 8a. The cells
showed typical charge–discharge curve with initial discharge
capacity of
145 mA h g1, and all of the cells demonstrated
capacity fading to some extent with the current rate increasing,
which were likely caused by the structural instability of LiCoO2
and side reactions during charge/discharge.46,57 Aer 50 cycles,
the capacity retention ratio of the PVA based cells for PVA-2%,
PVA-1% and PVA were about 93%, 90% and 86%, respectively,
higher than that of the PP cell (80%). Typically, PVA based cells
with larger content of CNF–Li demonstrated higher discharge
C-rate capacities which led to better long-term stability and
columbic efficiency in comparison to PP cells.
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Fig. 8 (a) Cycling stability of the cells with separators (b) discharge rate performance for the high mass loading LiCoO2 cathode.
Fig. 8b showed the PVA based cells also demonstrated better
performance than PP cells at higher charge/discharge current
densities. Capacity drop were observed with increasing C-rate in
all of the cells, resulting from the electrical polarization caused
by the increase in the serial resistance with increasing discharge
C-rate.29 The data demonstrated that the PVA based cells
exhibited much better C-rate capability. For example, the PVA
based cells kept specic capacity of 91.8, 82.3 and 73.8 mA h g1
at 4.0C, respectively, corresponding to 63%, 57% and 51% of
those at 0.2C; while that of the PP cell was only 56.7 mA h g1,
about 39% of that at 0.2C.
The improved cycle performance of the PVA based separators
may be attributed to the following reasons. On one hand, PVA
based separators with remarkable electrochemical stability and
highly developed microporous structure as well as strong
affinity between separator and electrolyte, which could result in
more facile ion transport and better interface stability during
cycling.29,53 On the other hand, the incorporation of CNF–Li
increased the amount of Li+ and opened a new way for Li+
transportation simultaneously which led to more facile ion
transport and less dendrite formation.38–40 Moreover, the larger
amount of CNF–Li with better mechanical properties led to
better resistance to lithium penetration.
Microporous structure, the addition of CNF–Li in PVA based
separators were sufficiently well-tuned to afford high ionic
conductivity, good electrolyte wettability and better mechanical
properties, which consequently contributes to superior
discharge performance for LIBs.
4. Conclusion
CNF–Li mannered with big respect ratio was successfully
prepared which possessed both admirable properties of cellu-
lose nanobers and ion-conductive polymer like CMC–Li with
groups of –COO–Li. PVA/CNF–Li based membrane for the
potential lithium-ion battery separators fabricated by the NIPS
wet-process presented excellent porosity, ionic conductivity and
remarkable electrolyte wettability. The introduction of CNF–Li
improved thermal stability, mechanical performance compared
with the commercial PP separator. Besides, CNF–Li as
a constituent increased the contents of Li+ and opened a way for
Li+ transportation, improving the diffusion efficiency and
specic capacity. The electrochemical characterization further
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conrmed the lithium-ion battery assembled with the PVA/
CNF–Li composite separator exhibited preferable comprehen-
sive performances, such as the cycle ability, C-rate capability
and thermal resistance, compared with the PP separator. In
summary, this novel and environment-friendly separator can
function as a high performance separator, resulting in a good
candidate for high performance LIBs.
Acknowledgements
This work was supported by the Municipal science and tech-
nology projects of Beijing [grant numbers Z141103004414111].
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