ORIGINAL PAPER
Properties of electrospun PVDF/PMMA/CA membraneas lithium based battery separator
Tusiimire Yvonne • Chuyang Zhang •
Changhuan Zhang • Edison Omollo •
Sizo Ncube
Received: 23 December 2013 / Accepted: 9 May 2014
� Springer Science+Business Media Dordrecht 2014
Abstract Poly vinylidene fluoride:poly methyl
methacrylate:cellulose acetate (CA) at ratios of
100:0:0, 90:10:0, 90:5:5 and 90:0:10 respectively,
were successfully electrospun. These membranes
were mixed to form a 12 wt% solution prepared with
volume ratio 7:3 of DMAc:acetone solvents. These
membranes were then analyzed using differential
scanning calorimetry, scanning electron microscopy,
FTIR, WAXD, pore size, porosity% and electrolyte
uptake (EU)%. It was observed that the best absorption
results were obtained in the presence of CA. The
electrospun membrane at ratio of 90:0:10 was
observed with the highest porosity of 99.1 % and EU
at 323 %. It also had a 43.6 % crystallinity and a
162 �C melting temperature. It was then concluded
that addition of CA improved the separator properties.
Keywords Cellulose acetate (CA) � Poly
vinylidene fluoride (PVDF) � Poly methyl
methacrylate (PMMA) � Electrospinning �Battery separator
Introduction
It is evident that there is continuous research being done
in improving specific electrochemical systems and
introducing new battery chemicals. Usually Lithium
based batteries use micro-porous membranes or non-
wovens separators made from polyolefin (Arora and
Zhang 2004) due to their many advantages. However
polyolefin materials like Poly vinylidene fluoride
(PVDF) have a number of short comings like poor
wettability, electrolyte leakage, low porosity and high
cost. A number of studies have been carried out in order
to improve the properties of PVDF and these have led to
modification methods such as blending, surface coat-
ing, surface grafting, heat treatment, pore filling and
sputtering being used in the production of modified
PVDF (Zhang 2007; Ding et al. 2009; Li et al. 2011;
Zhang et al. 2005; Ma et al. 2013; Takemura et al. 2005;
Liu et al. 2011; Cui et al. 2013). Studies of PMMA and
its properties in lithium batteries have been carried out
(Manuel Stephan and Nahm 2006) and these have led
to PMMA being blended with PVDF. The use of poly
methyl methacrylate (PMMA) as a possible electro-
lyte for lithium batteries was explored by Iljima et al.
(1985), Feuillade and Perche (1975), Appetecchi (1995)
T. Yvonne (&) � C. Zhang � C. Zhang �E. Omollo � S. Ncube
College of Textiles, Donghua University,
Shanghai 210620, China
e-mail: [email protected]
C. Zhang
e-mail: [email protected]
C. Zhang
e-mail: [email protected]
E. Omollo
e-mail: [email protected]
S. Ncube
e-mail: [email protected]
123
Cellulose
DOI 10.1007/s10570-014-0296-1
and Zhou et al. (2004). Although addition of PMMA in
PVDF brought about an increase in porosity, improved
absorption, low costs (Schneider et al. 2001),
enhanced ionic conductivity and improved elongation
at break, there was a decrease in crystallinity (Li et al.
2011; Ding et al. 2009). This decrease was attributed
to the hindrance by PMMA large side group during the
crystallization of PVDF (Ma et al. 2013; Tomura and
Inoue 1992).
With the growing environmental concerns (Padbury
and Zhang 2011), separators made with or blended with a
biodegradable polymer should be an added advantage to
the search of the ideal LITHIUM battery separator.
Cellulose acetate (CA) is widely used due to its high
strength, high stiffness, low weight and the added
advantage of biodegradability and renewability (Jabbour
et al. 2013a; Tseng et al. 2012). Cellulose based
derivatives have been successfully used in lithium
batteries (Lalia et al. 2012; Jabbour et al. 2013a, b;
Kritzer 2006) for the production of electrodes, separators
or as reinforcing agents in gel polymer or solid polymer
electrolytes (Jabbour et al. 2013a). Cellulose based
derivatives have also been successfully used in alkaline
batteries due to their excellent wettability, low processing
costs, high porosity, good mechanical properties and low
weight (Jabbour et al. 2013a; Zhou et al. 2011). CA based
separators have been successfully studied by Gozdz et al.
(2002), Rosso et al. (2006), Zhang et al. (2012), Ren et al.
(2009), and many others (Lee et al. 2010; Samad et al.
2013a; Lalia et al. 2012; Jabbour et al. 2013b). Therefore
a low cost readily available CA was introduced.
In this study, we investigated the battery separator
properties with the addition of CA. Membranes of
PVDF:PMMA:CA at ratios of 100:0:0, 90:10:0,
90:5:5 and 90:0:10 were electrospun and subjected
to tests. Electrospinning was used to manufacture the
separators because membranes produced using this
technique are often of high surface area, good surface
adhesion, high density pores, and large surface to
volume ratio and the three dimensional structure helps
in retaining liquid electrolyte (Subbiah et al. 2005).
Experimental
Materials
CA granules (MW = 30,000 g/mol, 39.8 % acetyl
content and degree of acetyl substitution of 2.5) were
purchased from Deng Wei Zhangmutou Plastics (China)
while PMMA powder was purchased from Alfa Aesar
China (Tiajin) Co., Ltd., PDVF (MW = 400,000 g/mol,
Kynar 761) was purchased from Arkema, France.
Acetone purchased from Changzhou Chemical Reagent
Co., (China). N,N-dimethylacetamide (DMAc) from
Shanghai Lingteng Chemical Reagent Co., Ltd., (China)
and n-butanol from Sinopharm Chemical Reagent Co.,
Ltd., and Electrolyte (EC/DMC1: 1 (W/W) LiPF6 1 mol/
l) from Zhangjiagang Guotai-Huarong New Chemical
Materials Co., Ltd., (China). All reagents were used
without further purification.
Membrane preparation
Solute mixtures of PVDF:PMMA:CA at weight ratios
of 100:0:0, 90:10:0, 90:5:5 and 90:0:10 were dissolved
into a mixed solvent of DMAc:acetone (7:3 by
volume) with a concentration of 12 wt%. The solu-
tions were stirred at room temperature for 24 h to
ensure a homogeneous mixture and degassed in
ultrasonic cleaner for 2 h to get a uniform solution.
The membranes were then prepared for a typical
electrospining arrangement. The solutions were fed
into the 10 ml syringe using a stainless steel needle of
0.514 mm inner diameter. The spinning rate was
0.8 ml/h under a potential difference of 16 kV gener-
ated at a distance of 20 cm from the cathode needle tip
to a grounded anode aluminum foil collector. The
relative humidity and the atmospheric temperature
were maintained at 60 ± 2 % and 21 ± 1 �C respec-
tively. The membranes were then dried at 60 �C for
24 h in a conventional oven to remove any solvent
residual before further use.
Characterization
Using Nicolet 6700 FTIR spectrometer (thermo Fisher
Scientific Inc.,), the FTIR data was obtained from each
sample and the side groups analyzed to verify the
polymer.
The surface morphology of the membranes was
observed under scanning electron microscopy (SEM)
on a TM3000 Tabletop Microscope Hitachi. The SEM
images were then analyzed using image analysis
software (Adobe Acrobat X Pro 10.1.2.45) to measure
the nanofiber diameters.
The thermal properties of the membranes were
analyzed using differential scanning calorimeter (DSC
Cellulose
123
704 F1 Phoenix, NETZCH. Germany) as described in
ASTM D 3418-03. The heating rate for the DSC
machine was set at 10 �C/min within a range of 50–
200 �C under nitrogen atmosphere. The crystallinity
(Xc) was calculated from heat enthalpies of electro-
spun membranes using Eq. 1.
Xc ¼DHf
DH�f� 100 % ð1Þ
where DHf is the PVDF based electrospun membrane
melting enthalpy (J/g) and DH�f is the melting enthalpy
for 100 % crystalline PVDF and has a value of
104.7 J/g (Li et al. 2011).
The wide-angle X-ray diffraction (WXRD, D/Max-
2550, RIGAKU, Japan) using Cu Ka radiation target,
tube voltage of 45 kV, tube current of 50 mA, scan
rate of 2�/min and the scanning range of 2h from 10� to
90� was used.
Pore size and distribution were obtained using the
automatic porometer (3G, Quantachrome Co., USA).
The samples were cut to a diameter of 25 mm before
analyzing the Pore sizes of the samples in their dry and
wet states. The liquid surface tension of 16.00 dynes/
cm was used for wetting.
Porosity % tests were done using the n-butanol
immersion method as described in ASTM D-2873.
The membrane samples were cut into 2 9 2 cm2,
thickness denoted as h and dry weight denoted Wd
before immersing them in n-butanol for 2 h. Excess
liquid was then carefully wiped off the sample surface
using a filter paper before measuring the weight
denoted as Ww. The porosity (P%) of the samples were
then calculated using Eq. 2.
P % ¼ Ww �Wd
qb � Vm
� 100 % ð2Þ
where qb is the density of n-butanol and Vm is fiber
membranes volume.
Electrolyte uptake measurements
For each membrane three samples were cut into discs
of 19 mm diameter. The dry weight measured and
denoted as Wo. The samples were then immersed into
the electrolyte solution for 3 h. Using a filter paper,
excess liquid was carefully wiped off the sample
surface of the sample and the weight was then
measured and denoted as W1. The electrolyte uptake
(EU)% was calculated using Eq. 3.
EU ¼ W1 �W0
W0
� 100 % ð3Þ
Results and discussions
SEM
The surface morphology of the electrospun blended
membranes was done using the SEM and the results
are shown in Fig. 1.
It was observed that with an increase in PMMA
content resulted in an increase in the diameter of the
produced nanofibers as shown in Fig. 2. However
addition of CA content resulted in fibers with a reduced
diameter as shown in Table 1. The highest and lowest
nanofiber average diameters were as 0.95 lm at
100:0:0 and 0.56 lm at 90:0:10 respectively. The
average nanofiber diameter and nanofiber distribution
are important factors in electrospun membranes.
FTIR
PVDF was identified as 1,178 cm-1 at C=F stretching
vibration strength (Li et al. 2011; Liu et al. 2011) as shown
in Fig. 3. This vibration was gradually strengthened to
1,182, 1,179 and 1,181 cm-1 in PVDF:PMMA:CA with
ratios of (b) 90:10:0, (c) 90:5:5 (d) 90:0:10 respectively.
PMMA and CA were both identified by C=O side
group. CA was identified as 1,748 cm-1 at C=O
stretching vibration observed in the CA granules (e).
At a ratio of 90:0:10 (d), C=O stretching vibration
shifted to 1,753 cm-1 due to the interaction with
PVDF. With addition of PMMA in the ratio 90:5:5,
C=O was shifted to 1,731 cm-1. This was because
C=O stretching vibration is also found in PMMA (Li
et al. 2011; Cui et al. 2013). PMMA was identified by
C=O presence at a vibration strength 1,729 cm-1 in
the ratio 90:10:0.
The above observations indicate that there were a
molecular level interactions between the polymers that
were present in the electrospun PVDF:PMMA:CA
membranes (Li et al. 2011).
DSC
As shown in Fig. 4, with the presence of PMMA and
CA there was a reduction in both the melting
temperatures (Tm) and crystallinity% as summarized
in Table 1.
Cellulose
123
The decrease in the Tm due to the presence of
PMMA was attributed to the hindrance of PVDF
crystallization due to the presence of the large group
CH3OCO– in PMMA chains (Ding et al. 2009; Ma
et al. 2013). The highest melting temperature for the
blended membranes was recorded as 161.8 �C at a
PVDF:PMMA:CA ratio of 90:0:10. This same blend
ratio showed the highest percentage of crystallinity of
43.6 %.
It was suggested that crystallinity does not have to
be modified, or only rarely modified for immiscible
blends (Bauduin et al. 1999). Therefore the slight
decrease in Tm in this study may be due to the high
immiscibility between PVDF and PMMA as com-
pared to that between PVDF and CA as well as the
large group side group found in PMMA. Low crystal-
line membranes are known to be beneficial in during
absorption.
WAXD
Figure 5 shows WXRD patterns for electrospun
PVDF:PMMA:CA membranes. It has been proved
that PVDF can exhibit five different polymorphs (a, b,
c, d and e) depending on the processing conditions
(Zheng et al. 2007). In Fig. 6, a very strong diffraction
peak for (a) is PVDF observed at 2h of 20.8�,
corresponding to 110 and 200 reflections of b. Other
membranes registered weak diffraction peaks at 36.6�and 41.7� related to 201 and 111 reflections of b phase
(a)
X 10k
(b) (c) (d)
X 10kX 8kX 8k
Fig. 1 SEM showing the surface morphology of PVDF/PMMA/CA at ratios of a 100:0:0, b 90:10:0, c 90:5:5 and d 90:0:10
0 400 800 1200 1600 2000 24000
20
40
60
80
100
120
Cou
nt
Fiber Diameter (nm)
(a)
0 200 400 600 800 1000 1200 1400 1600 18000
20
40
60
80
100
120
Cou
nt
Fiber Diameter (nm)
(b)
0 400 800 1200 1600 2000 24000
10
20
30
40
50
60
Cou
nt
Fiber Diameter (nm)
(c)
0 200 400 600 800 1000 1200 1400
0
10
20
30
40
Cou
nt
Fiber Diameter (nm)
(d)
Fig. 2 Fiber distribution graphs of PVDF/PMMA/CA at ratios of a 100:0:0, b 90:10:0, c 90:5:5 and d 90:0:10
Table 1 Data summary of PDVF/PMMA/CA membrane
PVDF:PMMA:CA Tm (�C) Melting
enthalpy (J/g)
Crystallinity (%) Average pore
size (lm)
Average fiber
diameter (lm)
Porosity (%) EU (%)
DSC WAXD
100:00:00 164.40 49.80 47.60 41.30 1.88 0.95 88.30 275.20
90:10:00 160.30 38.40 36.70 35.12 2.04 0.82 93.00 277.90
90:05:05 160.50 43.80 41.80 32.86 1.29 0.89 94.20 314.70
90:00:10 161.80 45.60 43.60 45.10 1.60 0.56 99.10 323.40
Cellulose
123
respectively (Kim et al. 2011). This dominance of b in
the electrospun membrane was attributed to the
disentanglement and parallel packing of polymer
chains creating orientation of the chains along the
fiber axis (Cui et al. 2013a).
There was a dominant peak that reflected bcorresponding to 110 and 200 in PVDF. Any addition
of PMMA and CA into the membrane did not cause a
position change in the major PVDF diffraction peak.
This indicated that there was no change in the crystal
structure of the electrospun membranes. Although
there is no change in crystal structure, the polymer
orientation and rearrangement of the crystalline state
was verified by the degree of crystallinity as shown in
Table 1.
Porosity and EU%
Porosity is important as it provides a reservoir for liquid
electrolyte in batteries. The three-dimensional network
structure of electrospun membranes enables easier in
penetration of liquids and thus absorption (Li et al.
2011). Porosity and EU% absorptions of the electrospun
membranes were observed to increase with addition of
PMMA and CA as shown in Figs. 6 and 7. The increase
in the porosity due to the presence of PMMA was
4000 3500 3000 2500 2000 1500 1000 500
% T
rans
mitt
ance
Wavenumber (cm-1)
(a) PVDF: PMMA:CA at 100:0:0 (b) PVDF: PMMA:CA at 90:10:0 (c) PVDF: PMMA:CA at 90:5:5 (d) PVDF: PMMA:CA at 90:0:10 (e) CA granules
(a)
(b)
(c)
(d)
(e)
C=O CF2
Fig. 3 FTIR graphs showing chemical groups of electrospun
membrane
60 80 100 120 140 160 180 200
(a) PVDF: PMMA:CA at 100:0:0 (b) PVDF: PMMA:CA at 90:10:0 (c) PVDF: PMMA:CA at 90:5:5 (d) PVDF: PMMA:CA at 90:0:10 (e) CA granules
Hea
t flo
w
Temperature ( C)
(e)
(d)
(c)
(b)
(a)
Fig. 4 DSC thermograms of electrospun membrane
0 20 40 60
Inte
nsity
(a) PVDF: PMMA:CA at 100:0:0 (b) PVDF: PMMA:CA at 90:10:0 (c) PVDF: PMMA:CA at 90:5:5 (d) PVDF: PMMA:CA at 90:0:10
Two-Theta(deg)
(a)
(b)
(c)
(d)
Fig. 5 WAXD patterns for electrospun membrane
100 0 0 90 10 0 90 5 5 90 0 100
20
40
60
80
100
PVDF: PMMA: CA membranes
Por
osity
(%)
88%93% 94%
99%
Fig. 6 Porosity of electrospun membrane
Cellulose
123
attributed to the large increase of amorphous regions
(Ma et al. 2013) as well as the increase in the surface area
(Li et al. 2011) attributed into the decrease in the average
nanofiber diameters of respective membranes. The
increase in porosity due to the presence of CA was
attributed to the absorption properties of cellulose based
membranes (Lalia et al. 2012; Jabbour et al. 2013a;
Zhang 2007; Mu et al. 2010).
According to Table 1, there was simultaneous
increase in porosity and electrolyte uptake of the
membrane. The highest values were observed within
the membrane with the highest CA weight ratio. The
affinity of the electrolyte to the CA groups is a very
important property for liquid lithium batteries.
Increase in EU% uptake in the presence of PMMA
can be explained as the electrolyte affinity of PMMA
that capture large amounts of liquid electrolyte (Cui
et al. 2013a) with contact.
There was an increase in EU% with the presence of
PMMA and CA as shown in 7. With an increase in CA
wt%, there was an evident increase in EU% from 315
to 323 % at a ratios of 90:5:5 and 90:0:10 respectively.
Increase of EU% due to the presence of CA was
attributed to the absorption properties of cellulose
based membranes (Lalia et al. 2012; Jabbour et al.
2013a; Zhang 2007; Mu et al. 2010). This also
explains the increase of porosity%.
Pore size
Membranes can easily absorb large amounts of
liquids. However, with large pore openings, these
liquids can easily be lost while removing the excess
liquids with filter paper (Kim 2005). This means that
high absorption of liquids does not mean high
retention of these liquids when the pore sizes are
large. This explanation should be true in the case of
90:10:00, where the pore size of 2.04 lm was the
highest registered. However due to the PMMA affinity
to liquids, there was substantial amount of retained
liquids as compared to 100 % PVDF with a lesser pore
size of 1.88 lm. Increase of absorption percentages in
both porosity% and EU%, regardless to the fluctuating
pore size was due to liquid affinity of both PMMA and
CA (Cui et al. 2013a; Mu et al. 2010).
Conclusion
Different weight ratios of PVDF:PMMA:CA mem-
branes were successfully electrospun. Melting mor-
phologies were shown to reduce with addition of
PMMA and CA, however the highest Tm of blended
membrane was shown at a ratio of 90:0:10 at 161.8 �C.
Crystallinity percentage in the electrospun membranes
were also observed at the weight ratio of 90:0:10 at
43.6 and 45.1 % shown by DSC and WAXD data
respectively. There was an increase in porosity and
electrolyte uptake in the blended membrane as com-
pared to the 100 % PVDF. The highest percentages
shown at 90:0:10 blend at 99.1 and 323.4 % for
porosity and electrolyte percentage respectively were
attributed to the absorption nature of cellulose based
membranes. These findings proved that addition of CA
brought about an improvement in membrane proper-
ties. Properties best suited for battery separators.
References
Appetecchi GB (1995) Kinetics and stability of the lithium
electrode in poly (methylmethacrylate)-based gel electro-
lytes. Electrochim Acta 40(8):991–997
Arora P, Zhengming Z (2004) Battery separators. Chem Rev
104(10):419–4462. doi:10.1021/cr020738u
Bauduin G, Boutevin B, Gramain P, Malinova A (1999)
Poly(vinylidene uoride)/poly(vinyl alcohol-co-vinyl ace-
tate) blends: 1. Compatibility Study by differential scan-
ning calorimetry (DSC). Eur Polym J 35:285–292
Cui W-W, Tang D-Y, Gong Z-L (2013a) Electrospun
poly(vinylidene fluoride)/poly(methyl methacrylate) graf-
ted TiO2 composite nanofibrous membrane as polymer
100 0 0 90 10 0 90 5 5 90 0 100
50
100
150
200
250
300
350
PVDF: PMMA: CA membranes
Ele
ctro
lyte
Upt
akte
(%
)
275% 278%
315%323%
Fig. 7 Electrolyte uptake of electrospun membrane
Cellulose
123
electrolyte for lithium-ion batteries. J Power Sources
223:206–213. doi:10.1016/j.jpowsour.2012.09.049
Cui Z, Drioli E, Lee YM (2013b) Recent progress in fluoro-
polymers for membranes. Prog Polym Sci. doi:10.1016/j.
progpolymsci.2013.07.008
Ding Y, Zhang P, Long Z, Jiang Y, Xu F, Di W (2009) The ionic
conductivity and mechanical property of electrospun P
(VdF-HFP)/PMMA membranes for lithium ion batteries.
J Membr Sci 329(1–2):56–59. doi:10.1016/j.memsci.2008.
12.024
Feuillade G, Perche P (1975) Ion-conductive macromolecular
gels and membranes for solid lithium cells. J Appl Elect-
rochem 5(1):63–69. doi:10.1007/BF00625960
Gozdz AS, Plitz I, Pasquier Du A, Red Bank (2002) Use of
electrode-bonded paper separators in non-aqueous slectric
double-layer capacitors and Li-ion batteries. In: Proceedings
of the 201st meeting of the Electrochemical Society, 12–17
Iljima T, Toyogushi Y, Eda N (1985) Quasi-solid organic
electrolytes gelatinized with poly-methyl methacrylate and
their applications for lithium batteries. Electrochem Soc
Jpn 53(8):619–623
Jabbour L, Bongiovanni R, Beneventi D (2013a) Cellulose-
based Li-ion batteries: a review. Cellulose 20:1523–1545.
doi:10.1007/s10570-013-9973-8
Jabbour L, Destro M, Chaussy D, Gerbaldi C, Bodoardo S,
Penazzi N, Beneventi D (2013b) Cellulose/graphite/carbon
fibres composite electrodes for Li-ion batteries. Compos
Sci Technol 87:232–239. doi:10.1016/j.compscitech.2013.
07.029
Kim JR, Choi SW, Jo SM, Lee WS, Kim BC (2005) Charac-
terization and properties of P(VdF-HFP)-based fibrous
polymer electrolyte membrane prepared by electrospin-
ning. J Electrochem Soc 152(2):A295. doi:10.1149/1.
1839531
Kim Y-J, Ahn CH, Lee MB, Choi M-S (2011) Characteristics of
electrospun PVDF/SiO2 composite nanofiber membranes as
polymer electrolyte. Mater Chem Phys 127(1–2):137–142.
doi:10.1016/j.matchemphys.2011.01.046
Kritzer P (2006) Nonwoven support material for improved
separators in Li–polymer batteries. J Power Sources
161(2):1335–1340. doi:10.1016/j.jpowsour.2006.04.142
Lalia BS, Samad YA, Hashaikeh R (2012) Nanocrystalline
cellulose-reinforced composite mats for lithium-ion bat-
teries: electrochemical and thermomechanical perfor-
mance. J Solid State Electrochem 17(3):575–581. doi:10.
1007/s10008-012-1894-1
Lee JM, Nguyen DQ, Lee SB, Kim H, Ahn BS, Lee H, Kim HS
(2010) Cellulose triacetate-based polymer gel electrolytes.
J Appl Polym Sci 115:32–36. doi:10.1002/app.29398
Li X, Cao Q, Wang X, Jiang S, Deng H, Wu N (2011) Prepa-
ration of poly (vinylidene fluoride)/poly (methyl methac-
rylate) membranes by novel electrospinning system for
lithium ion batteries. J Appl Polym Sci 122:2616–2620.
doi:10.1002/app.34401
Liu F, Awanis Hashim N, Yutie Liu MR, Abed Moghareh, Li K
(2011) Progress in the production and modification of
PVDF membranes. J Membr Sci 375(1–2):1–27. doi:10.
1016/j.memsci.2011.03.014
Ma T, Cui Z, Wu Ying, Qin S, Wang H, Yan F, Han N, Li J
(2013) Preparation of PVDF based blend microporous
membranes for lithium ion batteries by thermally induced
phase separation: I. Effect of PMMA on the membrane
formation process and the properties. J Membr Sci
444:213–222. doi:10.1016/j.memsci.2013.05.028
Manuel Stephan A, Nahm KS (2006) Review on composite
polymer electrolytes for lithium batteries. Polymer
47(16):5952–5964. doi:10.1016/j.polymer.2006.05.069
Mu C, Su Y, Sun M, Chen W, Jiang Z (2010) Remarkable
improvement of the performance of poly(vinylidene fluo-
ride) microfiltration membranes by the additive of cellu-
lose acetate. J Membr Sci 350(1–2):293–300. doi:10.1016/
j.memsci.2010.01.004
Padbury R, Zhang X (2011) Lithium–oxygen batteries—limit-
ing factors that affect performance. J Power Sources
196(10):4436–4444. doi:10.1016/j.jpowsour.2011.01.032
Ren Z, Liu Y, Sun K, Zhou X, Zhang N (2009) A microporous
gel electrolyte based on poly(vinylidene fluoride-Co-hex-
afluoropropylene)/fully cyanoethylated cellulose deriva-
tive blend for lithium-ion battery. Electrochim Acta
54(6):1888–1892. doi:10.1016/j.electacta.2008.10.011
Rosso M, Brissot C, Teyssot A, Dolle M, Sannier L, Tarascon
J-M, Bouchet R, Lascaud S (2006) Dendrite short-circuit
and fuse effect on Li/polymer/Li cells. Electrochim Acta
51(25):5334–5340. doi:10.1016/j.electacta.2006.02.004
Samad YA, Asghar A, Hashaikeh R (2013) Electrospun cellu-
lose/PEO fiber mats as a solid polymer electrolytes for Li
ion batteries. Renew Energy 56:90–95. doi:10.1016/j.
renene.2012.09.015
Schneider S, Drujon X, Wittmann JC, Lotz B (2001) Impact of
nucleating agents of PVDF on the crystallization of PVDF/
PMMA blends. Polymer 42(21):8799–8806. doi:10.1016/
S0032-3861(01)00349-4
Subbiah T, Bhat GS, Tock RW, Parameswaran S, Ramkumar SS
(2005) Electrospinning of nanofibers. J Appl Polym Sci
96(2):557–569. doi:10.1002/app.21481
Takemura D, Aihara S, Hamano K, Kise M, Nishimura T,
Urushibata H, Yoshiyasu H (2005) A powder particle size
effect on ceramic powder based separator for lithium
rechargeable battery. J Power Sources 146(1–2):779–783.
doi:10.1016/j.jpowsour.2005.03.159
Tomura H, Inoue T (1992) Light scattering analysis of upper
critical solution temperature behavior in a poly (vinylidene
fluoride)/poly (methyl methacrylate) blend. Macromole-
cules 25:1611–1614
Tseng H-H, Zhuang G-L, Su Y-C (2012) The effect of blending
ratio on the compatibility, morphology, thermal behavior
and pure water permeation of asymmetric CAP/PVDF
membranes. Desalination 284:269–278. doi:10.1016/j.
desal.2011.09.011
Zhang SS (2007) A review on the separators of liquid electrolyte
Li-ion batteries. J Power Sources 164(1):351–364. doi:10.
1016/j.jpowsour.2006.10.065
Zhang S, Xu K, Jow T (2005) An inorganic composite mem-
brane as the separator of Li-ion batteries. J Power Sources
140(2):361–364. doi:10.1016/j.jpowsour.2004.07.034
Zhang LC, Sun X, Hu Z, Yuan CC, Chen CH (2012) Rice paper as
a separator membrane in lithium-ion batteries. J Power
Sources 204:149–154. doi:10.1016/j.jpowsour.2011.12.028
Zheng J, He A, Li J, Han CC (2007) Polymorphism control of
poly(vinylidene fluoride) through electrospinning. Macromol
Rapid Commun 28(22):2159–2162. doi:10.1002/marc.2007
00544
Cellulose
123
Zhou YF, Xie S, Ge XW, Chen CH, Amine K (2004) Prepara-
tion of rechargeable lithium batteries with poly (methyl
methacrylate) based gel polymer electrolyte by in situ c-ray
irradiation-induced polymerization. J Appl Electrochem
34:1119–1125
Zhou W, He J, Cui S, Gao W (2011) Studies of electrospun
cellulose acetate nanofibrous membranes. Open Mater Sci
J 5:51–55
Cellulose
123