Polyphenols assisted silica coating on polypropylene separators with

improved wettability and heat-resistance for lithium-ion batteries

Jia-Jia Yuan, You-Zhi Song, Yin Zhang, Ze-Lin Qiu, Chuang-Chao Sun, Xue Yin, Li-Ping Zhu,
Bao-Ku Zhu
Key Laboratory of Macromolecule Synthesis and Functionalization (Ministry of Education), ERC of Membrane and Water Treatment
(Ministry of Education), Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, China
Correspondence to: B.-K. Zhu (E-Mail: zhubk@zju.edu.cn)

ABSTRACT: The separator, as one of the essential components for lithium-ion batteries (LIBs), has garnered considerable attention
because of its significant role in battery performance. Here, an in-situ coating method to promote the wettability and thermal-stability
of polypropylene (PP) separators was reported. The separator was first dip-coated with phenolic compound based on biologically
inspired surface modification. Then silica layers were in-situ formed on the separator via a sol–gel process of silicate solution, so that an
inorganic–organic hybrid layer was coated on PP separators without the need of any polymer binders. Besides, this method hardly
increases the film thickness or sacrifices microporous structure of the pristine separator. Due to the introduction of hybrid layers, the
resulted separators showed excellent dimensional thermostability, as the thermal shrinkage was only 20% at 150
C while that of the
bare separator was about 80%. Meanwhile, electrochemical performances of cells with the modified separator were obviously improved,
especially the rate performance. At the charge/discharge current density of 5 C, cells with PP separators nearly lost all the capacity, but
the modified separator still held 45.7% of the discharge capacity at 0.2 C. This facile yet effective method has great application prospects
in the preparation of ceramic-coated separators. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47277.

Received 5 July 2018; accepted 5 September 2018

DOI: 10.1002/app.47277

INTRODUCTION melt at elevated temperature, which will lead to short circuit,

Lithium-ion batteries (LIBs) have been widely applied in many
fields such as portable electronic devices, hybrid vehicles and
even fully electric vehicles since 1990s.1,2 Nowadays, consider-
able research efforts have focused on further enhancing LIBs
performance particularly the energy/power density, cycle life
and safety, due to the growing demand of advanced energy
storage devices.3–6 As one of the main components, separator
plays significant role in ensuring the cycling performance and
safety of LIBs.7–9 Commercial separators for LIBs are mainly
polyolefin-based microporous membranes such as polyethylene
(PE) and polypropylene (PP), thanks to their low cost, proper
pore structure, sufficient mechanical strength and excellent
electrochemical stability.10 However, polyolefin separators dem-
onstrate poor wettability and retention to conventional electro-
lytes due to their intrinsic hydrophobicity and low surface
energy. This characteristic may directly impair ions transport
and interface process, and consequently damage the cycle life
and rate performance of LIBs.11–13 Furthermore, polyolefin sep-
arators suffer from poor thermostability and may shrink and
unexpected thermal runaway and potentially cell explosion.14,15
Introduced an inorganic layer on the surface of polyolefin separa-
tor has proven to be an efficacious approach to improve both the
wettability and the thermostability owing to the excellent hydro-
philicity and heat resistant of inorganic materials.16,17 Jeong
et al. reported an inorganic/polymer/inorganic trilayer composite
separator. The close-packed SiO2 nanoparticles interconnected by
PVdF-HFP binders were coated onto PE separators, and the
composite separator showed reduced thermal shrinkage and
increased electrolyte uptake as expected.18 Similar researches that
coating inorganic particles (such as SiO2, Al2O3, TiO2, etc.) on
polyolefin separator surfaces using organic polymer (PVdF,
PVdF-HFP, PMMA, etc.) as binders have been reported.19–23
However, these methods cause some unfavorable results. First,
the thickness of ceramic-coated layers is generally up to several
microns, which will increase the cell weight and occupy the lim-
ited space of the full cell, and thus do harm to the specific energy
density of LIBs. Second, polymer binders may lead to pore block-
ing of separators, and that in turn reduce the ionic conductivity

Additional Supporting Information may be found in the online version of this article.
© 2018 Wiley Periodicals, Inc.

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and deteriorate the high-power capability of batteries.18 Besides,
it remains the risk that ceramic powders may detach from the
separator matrix during cell operation process attributed to poor
adhesion of binders. In addition, toxic organic solvents used dur-
ing the coating process will generate environmental problems.
Recently, some researchers noticed polyphenol’s strong adhesion
ability onto a variety of substrates, and tried to utilize the strong
adhesion capability of polyphenols to prepare ceramic-coating
separators.24–28 For example, Haeshin Lee et al. utilized polydo-
pamine to adhere SiO2 layers on PE separator surfaces, and the
binder-free silica coating increased the electrolyte wettability and
improved the thermal shrinkage of the pristine separators.26
However, these mussel-inspired ceramic coating processes may
be not suitable for commercial applications because of the high
cost, complicated operation and long time consuming. Pyrogallic
acid (1,2,3-trihydroxybenzene) is a kind of polyphenol which can
be found in many natural plants such as gallic acid and Eurasian
watermilfoil. It can react with amino groups in polyethyleneimine
(PEI) chains via Schiff base and Michael addition, and the reac-
tion products can quickly form a stable cross-linked layer on the
matrix surface.29 And the price of pyrogallic acid is much lower
than dopamine.
Hence, we reported a simpler and cheaper coating process that
using low cost pyrogallic acid (PG) as coating precursor to
replace dopamine and greatly simplifying the operation process.
In this work, SiO2-coated PP separators were fabricated via a
simple yet efficacious immersion of the pristine separators
sequentially into PG/PEI and ethylsilicate (TEOS) aqueous solu-
tion (Figure 1). This coating process is binder-free where silica
layers in-situ form on the separator surface, and it is environ-
mentally friendly because the entire process is accomplished in
aqueous media. Moreover, it is important that the silicification
reaction occurs throughout the entire separator because the
PG/PEI layers coat the “inner” and “outer” surfaces of separators.
Figure 1. (a) Schematic illustration of the preparation process. (b) Proposed mechanism of the inorganic–organic layers formation. [Color figure can be
viewed at wileyonlinelibrary.com]
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And the coating layers are so ultrathin that the separator thick-
ness hardly increases and the pore structure of PP separators is
well-preserved. Thus, the resulting separator exhibits not only
suppressed thermal shrinkage which resolve the safety issue, but
also superior electrolyte wettability thus improving the electro-
chemical performance of LIBs.
EXPERIMENTAL
Materials
Pyrogallic acid (PG, MW = 126.11, AR) and polyethylenimine
(PEI, branched, MW = 600 g/mol) were purchased from Aladinn
Chemistry Co. Ltd. (China). Tetraethoxysilane (TEOS) and etha-
nol were provided by Sinopharm Chemical Reagent Co. Ltd.
(China). All these chemicals were used without further purifica-
tion. Ultrapure water used in the experiments was obtained using
a Millipore water purification system (18.2 MΩ, Millipore, USA).
PP separators were supplied from Celgard Company (Celgard
2500, USA). Lithium cobalt oxide (LiCoO3), graphite, conductive
carbon black, polyvinylidene fluoride (PVDF), and other battery
materials were purchased from Shenzhen Ke-Jing Materials Tech-
nology Co. Ltd.
Coating Inorganic Layers on the PP Separator Surfaces
PP separators pre-wetted by ethanol were immersed into a
PG/PEI tris-buffer solution (pH = 8.5) with a respective concen-
tration of 1 mg/mL for 4 hours under stirred sustainedly. The
separators were then taken out, rinsed by ultrapure water for sev-
eral times and dried under ambient temperature. The pretreated
separators were named as PG-PP separators.
Coating Silica Layers on the PG-PP Separator Surfaces
The PG-PP separators were immersed into the mixture of TEOS,
water and ethanol (3:1:6 by weight) for 2 hours with stirring, and
a few drops of aqueous ammonia were added. Then, the separa-
tors were washed by ethanol-ultrapure water several times to
remove unstable affixed residues, and dried in a vacuum oven at
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47277

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60
C for 24 hours. The as-prepared separators were designated
as SiO2-PP separators.
Characterization
The functional groups on the surface of separators were con-
firmed by attenuated total reflectance fourier transform infrared
spectroscopy (ATR-FTIR, Nicolet 6700, USA) in a wavenumber
range of 4000–600 cm−1. The surface chemical composition of
separators was analyzed by X-ray photoelectron spectroscopy
(XPS, PHI5000, USA) with Mg Kα excitation radiation (hν =
1253.6 eV). The takeoff angle of the photoelectron was set at
60
, corresponding to the measured depth of about 10 nm. The
surface and cross section morphologies of separators were
observed on a field emission scanning electron microscopy (FE-
SEM, Hitachi S4800, Japan), and the element distribution were
examined by energy dispersive X-ray spectroscopy (EDX,
equipped with the FE-SEM). The air permeability of separators
was evaluated with a Gurley densometer (4110 N, Gurley, USA)
which could measure the time necessary for air to pass through
the substrates under a given pressure (i.e. a low Gurley value rep-
resents high air permeability). Weight gain percentage of separa-
tors compared with the pristine PP separator was calculated by
equation (1)
m1 −m0
weight gain percentage ðwt%Þ ¼ *100 ð1Þ
m0
where m1 and m0 are the weight of the modified separator and
the corresponding substrate, respectively. The electrolyte wettabil-
ity of separators was observed by the wettability test through
dropping a 10 μL liquid electrolyte on the separator surface and
confirmed by a contact angle analyzer (OCA20, Dataphysics,
Germany) equipped with video capture (the drop size was 3 μL).
The electrolyte uptake of separators was measured by immersing
the separators into liquid electrolyte for 1 hour and calculated
with equation (2)
W1 − W0
electrolyte uptake ðwt%Þ ¼ *100 ð2Þ
W0
where W0 and W1 represent the weight of the dry and the
electrolyte-soaked separator, respectively. The thermal resistance
of separators was evaluated with thermal shrinkage, which was
determined by measuring the dimensional change before and
after thermal treatment under 100–150
C for 1 hour. The degree
of thermal shrinkage was calculated by using equation (3)
Ai − Af
shrinkageð100%Þ ¼ *100 ð3Þ
Ai
where Ai and Af are the initial and final area of the separator after
the thermal treatment.
Electrochemical Characterization
The ionic conductivities of separators were measured by electro-
chemical workstation (CHI 660 C, China) with the stainless steel
(SS)/separator/SS cell at a frequency range of 1 Hz-100 kHz in
an AC mode. The ionic conductivity (σ) was calculated according
to equation (4)
L the pristine, PG-PP, and SiO2-PP separators was analyzed using
σ¼ ð4Þ
Rb  A
where Rb, L and A are the bulk impedance (ohm), thickness of
the separator (22 μm) and the effective area (1.96 cm2),
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respectively. The interfacial resistance (Rint) of separators was
measured with the cell assembly of lithium foil (Li)/separator/Li
at a frequency range of 1 Hz-100 kHz in an AC mode. The
impedance plots of the cells stored for different time were also
tested to study the Rint changes. The electrochemical stability was
investigated by the linear sweep voltammetry (LSV) test from
0 to 6 V (vs. Li/Li+) at a scan rate of 10 mV/s with the assembly
of SS/separator/Li.
The battery performance of separators was examined using 2016
coin-type cells. The separator was soaked with liquid electrolyte
and sandwiched between a LiCoO2 cathode and a graphite anode.
The cathodes of the test cells were prepared by slurry coating a
mixture of LiCoO2, carbon black, and poly(vinylidene fluoride)
(8:1:1, mass ratio) onto high purity aluminum foil which was
then dried and pressed. The anodes were prepared by slurry coat-
ing a mixture of graphite (90 wt%), carbon black (5 wt%), CMC
(1.5 wt%) and SBR (3.5 wt%) onto copper foil. The liquid elec-
trolyte (1 M) was prepared by dissolving LiPF6 in the mixed sol-
vent of ethylene carbonate, dimethyl carbonate, and ethylmethyl
carbonate (1:1:1, mass ratio). All the test cells were assembled in
a dry, argon-filled glove box. The assembled coin cells were
cycled on a testing system (Neware, CT-3008, China) in the volt-
age range of 2.75 to 4.2 V at various charge/discharge rates from
0.2 C/0.2 C (20 mA/g) to 5 C/5 C (500 mA/g) to test the rate
capability. For the cycle stability, the charge/discharge current
density was fixed at 1 C/1 C (100 mA/g).
RESULTS AND DISSCUSION
The preparation process and mechanism of the SiO2-PP separa-
tors is depicted in Figure 1. As Figure 1a shows, PP separators
were sequentially immersed into PG/PEI and TEOS aqueous
solution. In the first step, the PP separator was immersed into
PG/PEI aqueous solution, whereupon the reaction products of
PG molecules and PEI chains were adsorbed on the separator
skeleton to form a hydrophilic organic layer. In detail, PG mole-
cules were first oxidized by oxygen dissolved in the solution to
generate oxidative intermediates. The oxidized PG molecules
could be connected with the amino groups in PEI chains by cova-
lent bonds via reversible Schiff base and irreversible Michael
addition so that aqueous-insoluble products were formed
(Figure 1b).29 The products at the interface of solution and sepa-
rators would be adsorbed onto the surface of separator skeleton.
Then a stable cross-linked PG/PEI layer was formed on both the
outer- and inner-surfaces of the separator. In the second step,
TEOS could be easily hydrolyzed to form SiO2 particles under
catalysis of ammonium hydroxide.30 Meanwhile, SiO2 particles
could deposit on the PG/PEI layer due to the existence of pheno-
lic hydroxyl groups, and formed a thin inorganic layer on the
separator surface. The resulted SiO2-PP separator was finally
obtained.
To confirm the successful coating of inorganic–organic hybrid
layers onto PP separators, the surface chemical composition of
ATR-FTIR and XPS. ATR-FTIR spectra were shown in
Figure 2a. The bare separator exhibits characteristic absorption
peaks of PP polymer. For example, the peaks at 2951 cm−1 and
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47277

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Figure 2. (a) ATR-FTIR spectra and (b) XPS spectra of the PP, PG-PP, and
SiO2-PP separators. [Color figure can be viewed at wileyonlinelibrary.com]
2842 cm−1 correspond to the non-symmetric stretching vibration
of –CH3 and the symmetric stretching vibration of C − H,
respectively.7,31 For the PG-PP separator, that a broad peak
between 3600 and 3100 cm−1 representing the –OH stretching
vibration and a new peak at 1627 cm−1 ascribed to the C–O
stretching vibration appear demonstrates the successful introduc-
tion of PG/PEI layers.29,32 For the SiO2-PP separator, all the char-
acteristic peaks originating from the bare and the PG-PP
Figure 3. (a) The surface and (b) cross-section SEM images of the PP, PG-PP, and SiO2-PP separators.
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separators are still preserved, while some new peaks appear. The
most obvious peak at 1100 cm−1 is attributed to the stretching
vibration of Si − O − Si, indicating the formation of silica layers
on the separator surface.33 These results are consistent with XPS
spectra. As shown in Figure 2b, the bare separator just shows the
peak assigned to C 1 secondsecondsecondsecondsecondeconde-
condecondecond. For the modified separators, new peaks attrib-
uted to N 1 s, O 1 s, Si 2 seconds and Si 2p3 appear, further
confirming that the inorganic–organic coating on the surface of
PP separators was successful.
FE-SEM and EDX analyses were used to complement the struc-
tural information. The surface and cross-section SEM images of
the three separators are shown in Figure 3. It is clear to observe
numerous long and narrow parallel slit-like pores (500 nm in
length and 100 nm in width)on the surface of the pristine PP
separator. The surface porous structure remains almost
unchanged after coating with PG/PEI layers. For the SiO2-PP
ones, a few small particles can be observed on the separator sur-
face causing decrease of pore size. It should be pointed out that
although the surface pores get smaller, unwanted pore blockage is
not found, which can be demonstrated by the cross-section SEM
images and Gurley values as will be described below. As
Figure 3b shows, cross-section morphologies of the modified PP
separators barely change compared to the pristine ones. This
observation indicates that the hybrid layers do not block the
internal pores even though a few visible particles can be absorbed
on the separator surface. Concerning to the cross-section SEM
images, it must also be mentioned that the overall thickness of
the separators shows no significant increase after modification,
which is a distinctive advantage of this modified method com-
pared with conventional ceramic-coated separators. What’s more,
the uniform distribution of N, O, Si element observed by EDX
(Supporting Information, Figure S1) illustrates the successful
coating of PG/SiO2 layers on both the outer and inner surfaces of
the matrix. Importantly, the excellent flexibility of the pristine PP
separators does not disappear after modification. As exhibited in
Figure S2, the SiO2-PP separator is also easily bent.
Physical properties of the bare and modified PP separators were
shown in Table I. The permeability of the separators was evalu-
ated by Gurley value. As shown in Table I, Gurley value just
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Table I. Properties of the Bare, PG-Modified, and SiO2-Modified PP separator (0.56 mS cm−1). This difference may arise from the
Separators well-preserved pore structure (Figure 3) and enhanced wetting
capacity (Figure S3) of the porous substrates, which synergisti-
PP PG-PP SiO2-PP cally increase the electrolyte uptake and accordingly improve the
Weight gain / 4.0  0.4 5.5  0.5
ionic conductivity of PP separators.11 Electrochemical stability
(wt%) was tested by linear sweep voltammetry with SS/separator/Li
cells. According to the results shown in Figure S5, whether the
Gurley 246  10 248  10 266  5
bare separators or the modified separators exhibit an anodic sta-
value (s)
bility up to 4.4 V vs. Li/Li+, identifying that the PG/PEI and
Contact angles 46.5  1 15.0  1 14.9  0.7
SiO2/PG coatings possess reliable electrochemical stability.
(deg)
Electrolyte uptake 108  7 158  10 165  10 Interfacial resistance is a key parameter determining the electro-
(wt%) chemical performance of LIBs. Thus, electrochemical impedance
Bulk 2.00 1.77 1.70 spectra (EIS) were used to assess the interfacial properties.
impendence (Ω) Figure 4 displays the Nyquist plots of the Li/separator/Li cells.
Ionic conductivity 0.56 0.63 0.66
Obviously, the initial interfacial resistance of cells assembled with
(mS cm−1) the SiO2-PP separator is 240 Ω, which is lower than that of cells
assembled with the bare PP separator (470 Ω) and the PG-PP
separator (280 Ω). After stored for 7 days, the interfacial resis-
tance of cells with the PP separator and the PG-PP separator
increases slightly after each step of the modification process, fur- increases to 890 Ω and 440 Ω, respectively. In contrast, the cell
ther confirming that this modification method does not block the using the SiO2-PP separator shows much smaller resistance
internal pores of the separators. Besides, the weight gain percent- change (240 Ω after 1 day and 360 Ω after 7 days). These results
age is about 4.0% and 5.5% for the PG-PP and SiO2-PP separa- indicate that the SiO2-PP separator absorbed with liquid electro-
tors, respectively (Table. I). The slight increase in separator lyte has a much better compatibility with the electrodes, due to
weight indirectly implies that the coating layer on the separator its excellent electrolyte affinity and improved electrolyte uptake
skeleton is very thin, and thus barely affects the pore structure. (Table I). Besides, the Si − O units on the surface of the SiO2-PP
The reaction speed of TEOS hydrolysis reaction and SiO2 parti-
cles size mainly depend on the ammonia concentration and the
reaction time. So that we can control in-situ formation and depo-
sition process of SiO2 particles to thin the silica coating layer by
adjusting the solution concentration and the dip-coating time.
It was expected that the coating layer would improve the wetta-
bility of PP separators, so the hydrophilic characteristic of the
modified separators was described by the following observations.
As shown in Table. I, the electrolyte contact angle on the pristine
PP separator is 46.5  1
, whereas it drops to 15.0  1
and
14.9  0.7
on the PG-PP and SiO2-PP separators, respectively.
The better wettability can be attributed to the higher polarity and
surface energy after the modification. To describe it vividly, a
drop of electrolyte (10 μL) was dropped onto the separators
(Figure S3). We can observe that a liquid droplet is formed on
the surface of the pristine PP separator and the wetted area is
particularly small. But for the PG-PP and SiO2-PP separators,
they are absolutely wetted by the liquid electrolyte. Accordingly,
the liquid electrolyte uptake of the two modified separators with
enhanced wettability increases from 108  7% to 158  10% for
the PG-PP ones and 165  10% for the SiO2-PP ones.
Taking into account practical application of the modified separa-
tors, the effect of the hybrid layer on electrochemical properties
was discussed. First of all, the ion conductivity of separators was
measured by electrochemical impedance spectrum. The Nyquist
curves of SS/separator/SS cells are illustrated in Figure S4, of
which the high-frequency intercept on the real axis reflects the
corresponding bulk impendences (Rb). As shown in Table I, the
ion conductivity calculated using the equation (4) is 0.63 mS Figure 4. Nyquist plots of the Li/separator/Li cells assembled with the bare
cm−1 for the PG-PP separator and 0.66 mS cm−1 for the SiO2-PP and modified separators (a) after stored for 1 day and (b) after stored for
separator, which are both a bit higher than that of the bare 7 days. [Color figure can be viewed at wileyonlinelibrary.com]

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separator can work as Lewis acid centers to trap electrolyte
anions, thus delaying the oxidative decomposition of lithium salt
anions, which can also stabilize the interface.34
For practical battery testing, the charge–discharge measurements
of full cells (graphite/separator/LiCoO2) with different separators
were carried out. Figure 5a shows the charge–discharge profiles
of cells at the first cycle with the current density of 1C/1C. The
initial reversible capacities of cells with the pristine and PG-PP
separators are 120.9 mAh/g and 124.2 mAh/g, respectively, while
that of cells with the SiO2-PP separators is a bit higher (125.4
mAh/g). These results can be ascribed to the higher ionic con-
ductivity and the lower interfacial resistance. The cells’ cycle per-
formance at 1C was shown in Figure 5b. It can be clearly
observed that the discharge capacities decrease with increased
cycle number for all the cells, but the discharge capacity of cells
assembled with the SiO2-PP separators drops more slowly and
smoothly. After 100 cycles, the discharge capacities of cells with
the bare and PG-PP separators drop to 89.2 mAh g−1 and 99.3
mAh g−1, respectively, while that of the SiO2-PP separators is
104.3 mAh g−1. Besides, the capacity retention of cells assembled
with the SiO2-PP separators (retaining 83.2% of its initial dis-
charge capacity) is also higher than that of the bare (73.7%) and
PG-PP ones (80.0%). Figure 5b also gives the Coulombic effi-
ciency curves at 1C. Coulombic efficiency is defined as the ratio
of the discharge capacity to charge capacity, and the initial Cou-
lombic efficiency is usually very small. This is because the electro-
lyte decomposition and formation of solid electrolyte interphase
Figure 5. (a) Charge–discharge capacity of the first cycle for cells assembled
with different separators and (b) Cycle performance and Coulombic effi-
ciency of cells assembled with different separators. [Color figure can be
viewed at wileyonlinelibrary.com]
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Figure 6. Rate performances of cells assembled with different separators.
[Color figure can be viewed at wileyonlinelibrary.com]
(SEI) mostly occur during the first cycle. And thus some lithium
ions consumed by these reactions won’t contribute to the follow-
ing charge/discharge cycling, resulting in a loss of discharge
capacities. One noteworthy finding is that cells with the SiO2-PP
separators exhibit a higher initial Coulombic efficiency (96.5%)
compared to that using the pristine (94.9%) and PG-PP ones
(95.2%). This may be explained as that the better electrolyte affin-
ity of SiO2-PP separators and the stabilization of electrolyte
anions by Si-O units is beneficial to form SEI more efficiently
and therefore reduce the consumption of lithium ion.35 What’s
more, cells assembled with the SiO2-PP separators demonstrate a
more smoothly and relatively higher Coulombic efficiency com-
pared to that of the other two separators. In sum, these outstand-
ing characteristics of the SiO2-PP separator, such as better
electrolyte affinity and lower interfacial resistance, play a positive
role in improving the cycle stability and discharge capacity of the
cells, implying the feasibility of the modified separator in LIBs
practical application.
The modified separators were further tested focusing on the dis-
charge rate capability. The cells (graphite/separators/LiCoO2)
were charged/discharged at various current densities (from 0.2 C
to 5 C) under a voltage range between 3.0 and 4.2 V. As shown
Figure 7. (a) Thermal shrinkage of the PP and SiO2-PP separators stored at
different temperatures for 1 hoursoursourourour. [Color figure can be
viewed at wileyonlinelibrary.com]
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Figure 8. The surface SEM images of the SiO2-PP separators before and after being stored at 150
C and 180
C for 1 h.
in Figure 6a, the discharge capacity gradually decays with the
increase of discharge current density for all the cells, and capacity
retention (i.e. the ratio of retained discharge capacity to the dis-
charge capacity at 0.2 C) is to evaluate rate performance of the
cells. Obviously, the SiO2-PP separator reveals enhanced capacity
retention compared with the other two separators, especially at
higher current densities. For example, at the current density of
5 C, the SiO2-PP separator holds 45.7% of the discharge capacity
at 0.2 C, whereas the bare and PG-PP ones only maintain 18.2%
and 27.6% capacity, respectively. It is generally accepted that con-
ventional ceramic coatings would sacrifice the rate capability
because pore blocking resulting from polymer binders may hin-
der ionic diffusion.36 However, for the SiO2-PP separators, the
higher ion conductivity and the smaller interfacial resistance
achieved by hybrid thin layer coatings is likely to inspire faster
mobility and diffusion of Li-ions. Moreover, Si-O units on the
coating layers may trap electrolyte anions to reduce the polariza-
tion caused by the counteranions. Overall, the SiO2-PP separator
shows much better rate performance, which is greatly useful for
practical applications.
More importantly, thermal stability of separators is an essential
issue pertaining to battery safety, because it is inevitable to gen-
erate heat during cell cycling especially in the case of high
power output. To quantitatively analyze the influence of the
hybrid coatings on thermal resistance of the separators, thermal
shrinkage was tested by keeping 4 cm × 4 cm separators inside
an oven with designated temperature for 1 hour. As shown in
Figure 7, for the pristine PP separator, shrinkage becomes very
severe at higher temperature, and is up to 78% of the original
size when temperature rises to 150
C. Notably, the SiO2-PP
separator shows a reduced thermal shrinkage over the tempera-
ture range from 100
C to 150
C. And the thermal shrinkage
of the SiO2-PP separator is only 20% at 150
C, which verifies
that the introduction of the hybrid layers can suppress thermal
shrinkage of PP separators effectively. The result is surprising in
that the inorganic–organic layers are much thinner compared to
traditional ceramic coatings, but still leads to dramatic improve-
ment of the thermal stability, which may favor from the uni-
formly thin layers on the matrix skeleton working as a
protective layer to resist the dimensional variation at high
temperature.
Meanwhile, the shutdown function of separators also plays a sig-
nificant role in battery safety, which means separators would
close the pores to stop battery working while keeping the skeleton
from melting at high temperature. So the SEM images of the
SiO2-PP separator treated under different temperatures were car-
ried out. As can be seen from Figure 8, most pores remain their
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original structure at 150
C, and all of them close at 180
C, indi-
cating that the SiO2-PP separator can realize shutdown function
at high temperature. Taking the above observations into account,
the SiO2-PP separators have great potential as separators for
safety reinforced lithium ion battery according to their promoted
thermal resistance and shutdown function.
CONCLUSIONS
In this work, a facile and environmentally friendly process that
triggers the formation of inorganic–organic layers on PP separa-
tor surfaces was developed. The as-prepared separator displayed
increased ionic conductivity and reduced interfacial resistance
due to the enhanced wettability and electrolyte uptake, which in
turn improved the cell electrochemical performance particularly
the rate performance. Furthermore, the separator also exhibited
significantly improved dimensional thermostability without an
increase in the total thickness or pore blocking of the primitive
separator. Thus, we believe that the SiO2-PP separator with these
excellent properties would have more hopeful prospects in next-
generations high-performance LIBs.
ACKNOWLEDGMENTS
The authors declare no competing financial interests. This work
was supported by the National 863 Program of China (grant
number 2012AA03A602), the National 973 Program of China
(grant number 2009CB623402), the Nature Science Foundation
Committee of China (grant number 20974094) and Zhejiang Pro-
vincial Collaborative Innovation Center Program 2011 (grant
number G1504126001900).
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