Radiation Physics and Chemistry 132 (2017) 65–70

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Radiation Physics and Chemistry

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

Preparation of nanocomposite γ-Al2O3/polyethylene separator crosslinked MARK

by electron beam irradiation for lithium secondary battery
⁎
Young-Chang Nho , Joon-Yong Sohn, Junhwa Shin, Jong-Seok Park, Yoon-Mook Lim,
Phil-Hyun Kang
Research Division for industry & Environment, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil,
Jeongeup-si, Jeollabuk-do 56212, Republic of Korea

A R T I C L E I N F O A BS T RAC T

Keywords: Although micro-porous membranes made of polyethylene (PE) offer excellent mechanical strength and chemical
Lithium secondary battery stability, they exhibit large thermal shrinkage at high temperature, which causes a short circuit between positive
γ-Al2O3 and negative electrodes in cases of unusual heat generation. We tried to develop a new technology to reduce the
Separator thermal shrinkage of PE separators by introducing γ-Al2O3 particles treated with coupling agent on PE
Radiation
separators. Nanocomposite γ-Al2O3/PE separators were prepared by the dip coating of polyethylene(PE)
Electron beam irradiation
separators in γ-Al2O3/poly(vinylidenefluoride-hexafluoropropylene) (PVDF-HFP)/crosslinker (1,3,5-trially-
1,3,5-triazine-2,4,6(1 H,3 H,5 H)-trione (TTT) solution with humidity control followed by electron beam
irradiation. γ-Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE separator showed the highest electrolyte uptake
(157%) and ionic conductivity (1.3 mS/cm). On the basis of the thermal shrinkage test, the nanocomposite γ-
Al2O3/PE separators containing TTT irradiated by electron beam exhibited a higher thermal resistance.
Moreover, a linear sweep voltammetry test showed that the irradiated nanocomposite γ-Al2O3/PE separators
have electrochemical stabilities of up to 5.0 V. In a battery performance test, the coin cell assembled with γ-
Al2O3/PVDF-HFP/TTT-coated PE separator showed excellent discharge cycle performance.

1. Introduction high temperature, which may cause a short circuit between electrodes
(Gwon et al., 2009). They also have a weakness of wettability towards
Lithium-based batteries are widely used for portable electronics, electrolyte due to their inherent hydrophobic properties.
mobile products and communication devices because of their higher To improve the thermal property of polyolefin separators, polymer
energy density than other batteries (Takemura et al., 2005). A typical layers such as poly(vinylidene fluoride), poly(acrylonitrile) and poly(-
lithium ion battery consists of a positive electrode, a negative electrode, methacrylate) or coating with inorganic powders such as SiO2, Al2O3,
a separator, and a non-aqueous liquid electrolyte (Djian et al., 2007). A TiO2, MgO onto them have been studied. This approach has attracted
separator placed between a positive electrode and a negative electrode increasing attention because of its effectiveness in improving wett-
is one of the important components in rechargeable lithium batteries. ability and preventing the thermal shrinkage (Dong et al., 2016; Chen
It plays a crucial role in transporting ionic charge carriers between two et al., 2016; Song et al., 2012).
electrodes and preventing the electric contact between two components Although the coating process with inorganic particles is applied to
(Arora et al., 2004). Thus, it requires higher mechanical, chemical, and polyolefin separators, mechanical breakdown of polyolefin is not
electrochemical properties. Separators with enhanced thermal stability avoidable in at temperature above the melting point of polyolefin.
and good wettability in organic liquid electrolytes are desirable for the There have also been problems like the detachment between the
development of a safe and efficient lithium ion battery (Cho et al., coating layer and the polyolefin separator, and the separation of
2007; Lee et al., 2009; Cheng et al., 2004). particles from coating materials as well as the agglomeration of
Micro-porous polymeric membranes made of polyethylene (PE), inorganic particles. The inorganic particles have a strong tendency to
polypropylene (PP), and laminates of PE and PP are widely used as undergo agglomeration followed by insufficient dispersal properties of
separators in lithium-based non-aqueous batteries. Among them, PE the nanoparticles in polymer matrix.
membranes have been applied for separators of most lithium ion Truong et al.(2010) investigated the dispersibility of silane-functio-
batteries (Kostecki et al., 2004). However, PE membranes shrink at nalized alumina nanoparticles in syndiotatic polypropylene. Yang et al.

⁎
Corresponding author.

http://dx.doi.org/10.1016/j.radphyschem.2016.12.002
Received 10 August 2016; Received in revised form 8 November 2016; Accepted 3 December 2016
Available online 06 December 2016
0969-806X/ © 2016 Published by Elsevier Ltd.
Y.-C. Nho et al. Radiation Physics and Chemistry 132 (2017) 65–70

(2009) examined the surface properties of an untreated alumina and 2.3. Physical tests of nanocomposite γ-Al2O3/PE separators
alumina treated with four types of coupling agents.
The use of ionizing radiation to modify polymers and to improve The nanocomposite γ-Al2O3/PE separators were dried and sputter-
material properties is well known (Charlesby, 1960; Woods et al., coated with a thin gold film prior to SEM observation The morphol-
1994). For example, electron beam and gamma irradiation are widely ogies of the prepared separators were observed using Scanning
used to crosslink PE such as cable and wire insulation, tubing, films, Electron Microscopy (SEM, Jeol JSM-6390).
and fibers are sometimes irradiated at doses about 100 kGy to cause The liquid electrolyte uptake was determined by soaking the
crosslinking of polymer chains to improve properties such as mechan- obtained separators in a liquid electrolyte solution (1 M LiClO4 in
ical strength, thermal resistance, flame retardancy, and chemical EC/DEC (1:1 v/v)) for 24 h. To remove the excess electrolyte adhering
resistance. After radiation crosslinking, the PE has significant gel to their surfaces, the equilibrated samples were blotted using labora-
content. tory wipes and then weighed quickly. The liquid electrolyte uptake was
To increase affinity toward liquid electrolytes and lower the thermal determined from the difference in the weight of the dry samples and
shrinkage of PE separators, we used the new coating technology and their swollen counterparts. All the procedures were carried out in an
radiation. To prepare the coating solution for PE separators, PVDF- Ar-filled glove box (less than 5 ppm O2 and H2O).
HFP and TTT as a crosslinker were dissolved in acetone at room The ionic conductivity of the separators soaked with the electrolyte
temperature. Surface-treated γ-Al2O3 was then put in this prepared solution at room temperature was determined using an AC impedance
solution. PE separators were dip-coated, and then dried under with technique over the frequency range of 0.01–100 kHz using a Solatron
humidity condition, followed by electron beam irradiation. γ-Al2O3 SI 1260 frequency response analyzer combined with an SI 1287
powders were treated with coupling agent to increase their dispersi- electrochemical interface at a constant potential of 10 mV. The samples
bility in coating solution. It is important that the coated layers of the with area of A and thickness of L were sandwiched between two
separators have high porosity structures. There are several ways to stainless steel blocking electrodes to measure their electrolyte resis-
prepare porous membranes, such as sintering, stretching, track etching tance (Rb, Ω). The conductivity (σ, S/cm) was then calculated from Eq.
and phase separation process (Lloyd et al., 1990). The phase separation (1).
process can be achieved by immersing the polymer solution in a non- σ = L /(Rb A) (1)
solvent (diffusion induced phase separation). Non-solvent induced
phase separation is the most common method for fabricating PVDF The prepared separators were cut into 4 cm×4 cm pieces, and then
membranes with the desired porosity and pore structure. In this subjected to a thermal shrinkage. Thermal shrinkages were determined
system, phase inversion is achieved under humidified conditions, that by measuring the dimensional change after heating the samples in a
is, humidity acts as a non-solvent. forced convection oven at 150 °C for 1 h.
After coating process, radiation irradiation was employed to induce To investigate the linear sweep voltammetry, a virgin PE separator
the crosslinking of coated layer and PE separator. and the coated PE separators were soaked in a liquid electrolyte solution
consisting of 1.0 M LiClO4 in a 1:1 (v/v) ethylene carbonate (EC)/diethyl
carbonate (DEC) mixture. Then, the soaked separators were sandwiched
2. Experimental
between lithium metal and stainless steel, and assembled into a tightly
sealed test cell. The linear sweep voltammetry of the assembled test cells
2.1. Materials
was measured in the range of 3–5.5 V at 5 mV/s.
A lithium-ion cell was assembled by sandwiching the prepared
A commercial microporous PE separator (SKLiBS, thickness:
separator between a meso-phase carbon micro bead (MCMB) anode
12 μm) was supplied from SK Energy (Korea). and a LiCoO2 cathode after immersing them in the liquid electrolyte.
Poly(vinylidenefluoride-hexafluoropropylene) (PVDF-HFP) and
The cathode was composed of 94 wt% of LiCoO4 as a positive active
(1,3,5-trially-1,3,5-triazine-2,4,6(1 H,3 H,5 H)-trione (TTT) as a cross- material, 3 wt% of PVDF as a binder, and 3 wt% of super-P carbon as a
linker were purchased from Aldrich and used as received. An electro-
conductive agent. The anode consisted of 93.5 wt% of MCMB as a
lyte solution consisting of a 1.0 M of LiClO4 in 1:1 (V/V) ethylene negative material, 6 wt% of PVDF as a binder and 0.5 wt% of super-P
carbonate (EC) /diethyl carbonate (DEC) mixture was obtained from
carbon as a conductive agent. The cell was enclosed in a 2032-type coin
Techno-Semichem Co., Ltd. (Korea). γ-Al2O3 (size: 400 nm) was cell. All assembly procedures of the cells were carried out in a dry box
purchased from Buehler (USA). 3-(trimethoxysilyl)propylmethacrylate
filled with argon gas. The discharge cycling tests of the lithium-ion
(TMSPMA) and xylene were obtained from Sigma-Aldrich. Other
polymer cells were conducted using Toyo battery test equipment
solvents were regent grade and used as received. (TOSCAT-3000U). The charging process was terminated at an end
current of approximately 0.02 C rate (0.06 mA). The discharge current
2.2. Preparation of nanocomposite γ-Al2O3/PE separators was fixed to a constant-current value with an end voltage of 3.0 V. The
rest time was fixed to about 20 min between charge and discharge
γ-Al2O3 was treated with TMSPMA in xylene (TMSPMA/xylene: mode. All measurements were performed at room temperature.
90/10 v%) at 135?for 24 h.
To prepare the coating solution for PE separators, PVDF-HFP and 3. Results and discussion
TTT as a crosslinker were dissolved in acetone at room temperature.
Surface-treated γ-Al2O3 was then put in this prepared solution, and 3.1. Treatment of γ-Al2O3 particles with coupling agent
uniformly dispersed by ball milling overnight. The weight ratio of the γ-
Al2O3/PVDF-HFP/TTT mixtures was 90/10/0, 90/10/2, and 95/5/2. It is known that the combination of γ-Al2O3 particles and polymers
Nanocomposite γ-Al2O3/PE separators were prepared by dip coat- can improve the mechanical properties and thermal stability of
ing of PE separators in the above prepared solution and exposing them polymers for use under extreme conditions (Kim et al., 2010; Jirawat
to humidified conditions (Relative Humidity 40%) followed by electron et al., 2014; Giulio et al., 2010; Sohn et al., 2008).
beam irradiation (Sohn et al., 2009), where coated-separators sealed in A good adhesion and dispersion between two systems is one of the
laminated aluminum /PE films were irradiated using a conventional key factors determining the properties of the final products because the
1 MeV electron beam accelerator (EB-tech Co. Ltd., Daejeon, Korea) at particles have a natural tendency to agglomerate due to the specific
a radiation dose of 150 kGy, at a dose rate of 10 kGy/pass at room surface area and volume effects. One possible solution is to modify the
temperature. surface of the particles by treating them with a proper coupling agent to

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Y.-C. Nho et al. Radiation Physics and Chemistry 132 (2017) 65–70

Silylated Al2O3 Al2O3

Al2O3

TMSPMA

Silylated alumina
4000 3600 3200 2800 2400 2000 1600 1200 800
-1
Wave Number (cm )
Fig. 1. Typical FT-IR spectra γ-Al2O3, 3-(trimethoxysilyl)propylmethacrylate
(TMSPMA), and γ-Al2O3 treated with TMSPMA.
(a) (b)

promote the interaction between particles and polymers, and decrease Fig. 2. The state of dispersion of the surface-treated γ-Al2O3 particles (a), and non-
treated γ-Al2O3 particles (b) in PVDF-HFP and TTT solution involving acetone as a
the affinities between particles.
solvent.
In this experiment, γ-Al2O3 particles were put in a TMSPMA
coupling agent in xylene kept at 135 °C and then uniformly dispersed
by ball milling overnight for 24 h. FT-IR was used to confirm the γ- causes an internal electric shortage of the lithium battery, measuring
Al2O3 particles treated with a TMSPMA coupling agent (Fig. 1). For the the thermal shrinkage is very important for evaluating the thermal
virgin γ-Al2O3, besides the large band in the wave number range of stability of the prepared separators (Sohn et al., 2008). Fig. 4 shows the
500–900 cm−1, broad bands at 3434 cm−1 are due to the stretching thermal shrinkage of the virgin PE separator and γ-Al2O3-coated PE
vibration of the associated hydroxyl due to water absorption. After separators. A non-treated PE separator showed a huge thermal
treatment, new absorption bands appearing at 1715 cm−1 may be shrinkage of 76%, while a γ-Al2O3/PVDF-HFP/TTT (90/10/2)-coated
attributed to the stretching vibration of carbonyl groups, while the one PE separator ( ‘cʼ in Fig. 4), and a γ-Al2O3/PVDF-HFP/TTT(95/5/2)-
around 1637 cm−1 may be attributed to acrylic double bonds (C˭C). coated PE separator (‘dʼ in Fig. 4) showed no measurable shrinkage.
Moreover, the C-H alkyl stretching band is evidenced in the 2894– However, a considerable shrinkage was observed when crosslinking
2956 range. From these spectrums, we can confirm that γ-Al2O3 agent (TTT) was not added to the coating solution involving γ-Al2O3
particles were successfully treated with a TMSPMA coupling agent. particles (‘bʼ in Fig. 4), indicating that the crosslinking agent(TTT) in
PVDF-HFP plays an important role in increasing the thermal stability
of the separators (Andersson et al., 2015; Mitomo et al., 2005).
3.2. Preparation and SEM images of nanocomposite γ-Al2O3/PE
Although the irradiation of an electron beam can cause crosslinking
separators
of both PVDF-HFP (Medeirros et al., 2015; Karabelli et al., 2015) and
PE separator itself, it is assumed that TTT accelerates crosslinking of
For introducing γ-Al2O3 particles onto PE separators, the surface-
PVDF-HFP as well as the binding of silylated γ-Al2O3 particles with
treated and non-treated γ-Al2O3 particles were mixed with PVDF-HFP
PVDF-HFP because γ-Al2O3 particles treated with TMSPMA have vinyl
and TTT solution involving acetone as a solvent. As shown in Fig. 2, the
groups to crosslink PVDF-HFP by irradiation. PE separator itself had a
surface treatment can lead to an enhanced dispersion of γ-Al2O3
51 gel % when exposed to irradiation dose of 150 kGy, and PVDF-HFP
particles in PVDF-HFP/TTT solution, while non-treated γ-Al2O3 has
involving TTT had 42 gel % under the same dose, while PVDF-HFP
a tendency to agglomerate.
without TTT had 7 gel % under the same dose.
Nanocomposite γ-Al2O3/PE separators were prepared by dip-coat-
ing PE separators in the above PVDF-HFP and TTT solution involving
3.4. Electrical properties of nanocomposite γ-Al2O3/PE separators
γ-Al2O3, and then exposing them to humidified condition followed by
electron beam irradiation. The coated layer in the separators prepared
Fig. 5 shows the ionic conductivity of the virgin polyethylene
with a composition of γ-Al2O3/PVDF-HFP/TTT was observed using a
separator and the coated separators with various coating composition.
SEM technique. Fig. 3 shows SEM images of the surface and the cross
The ionic conductivity of the coated separators was higher in compar-
section of γ-Al2O3/PVDF-HFP/TTT-coated PE separators. As shown in
ison to that of the virgin polyethylene membrane. In particular, the γ-
Fig. 3, the coated layers of the separators have high porosity structures.
Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE separator exhibited a high-
In this system, phase inversion is achieved under humidified condi-
er ionic conductivity (1.3 mS/cm). Generally, the ionic conductivity is
tions, that is, humidity acts as a non-solvent. The porosity of the
dependent on the liquid electrolyte uptake. Thus, this high ionic
separator of a lithium-ion battery is an extremely important property
conductivity can be attributed to an increase in the liquid electrolyte
since the pores of the separator provide the space for electrolytes and
uptake caused by a high content of γ-Al2O3 and more pores on the
lithium-ion movement between anode and cathode for a current
coating layer compared to a virgin sample. The increase in the
generation.
amorphous domain in coating layer can also hold more liquid electro-
lyte.
3.3. Heat resistance of nanocomposite γ-Al2O3/PE separators The electrochemical stability of the separator at the range of
operating voltage in a lithium ion battery is important for practical
Since the thermal shrinkage of a separator at high temperature application. The electrochemical stability of the test cells containing a

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Y.-C. Nho et al. Radiation Physics and Chemistry 132 (2017) 65–70

Fig. 3. SEM images of surface of virgin PE separator (a), surface of Al2O3/PVDF-HFP/TTT(95/5/2)-coated PE separator (b), the cross-section of the γ-Al2O3/PVDF-HFP/TTT(95/5/2)-
coated PE separator (c), and the magnified cross-section of the coated layer in c (d).

160
1.2
150

Electrolyte Uptake (%)

Ionic Conductivity (mS/cm)

1.0
a b c d 140
0.8
130
0.6
120
0.4
Before thermal shrinkage 110
0.2
100
0.0
a: PE separator b c d

a b c d Fig. 5. The electrolyte uptake (dot) and ionic conductivities (bar) of PE separator (a), γ-
Al2O3/PVDF-HFP(90/10)-coated PE separator (b), γ-Al2O3/PVDF-HFP/TTT(90/10/2)-
coated PE separator (c), and γ-Al2O3/PVDF-HFP/TTT(95/5/2)-coated PE separator (d).

an electrolyte of lithium ion batteries operated at high voltage.

After thermal shrinkage To evaluate the effects of the γ-Al2O3/PVDF-HFP/TTT-coated PE
separator on the electrochemical performance of the lithium-ion
Fig. 4. Thermal shrinkage images of PE separator (a), γ-Al2O3/PVDF-HFP(90/10)- polymer cells, several coin type cells composed of a coated separator,
coated PE separator (b), γ-Al2O3/PVDF-HFP/TTT(90/10/2)-coated PE separator (c),
electrolytes, a LiCoO2 cathode, and a graphite anode were assembled
and γ-Al2O3/PVDF-HFP/TTT(95/5/2)-coated PE separator (d).
and subjected to battery performance tests. For the preconditioning
cycle, cut-off voltages of 4.2 V for the upper limit and 3 V for the lower
γ-Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE separator and virgin limit at a 0.1 C rate (0.3 mA) were employed for the first two cycles
polyethylene separator was evaluated using linear sweep voltammetry, prior to the rate capability measurements. After a preconditioning
and the results are presented in Fig. 6. It is clearly seen from Fig. 6 that cycle, the cells were charged at a current density of 1.5 mA (0.5 C rate)
the cell containing the γ-Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE up to a target voltage of 4.2 V. This was followed by a constant voltage
separator was stable up to 5.0 V in comparison with that of the PE charge with a decline of the current until the final current reached 20%
separator. Therefore, the ceramic-coated separator can be applicable to (0.02 C) of the charging current, and was then discharged down to a

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Y.-C. Nho et al. Radiation Physics and Chemistry 132 (2017) 65–70

0.5 C. However, as the C-rate increased from 1 C to 2 C, the relative

discharge capacities of the cells assembled with the virgin PE separator
began to decrease more than those of the cells with the γ-Al2O3/PVDF-
HFP/TTT-coated PE separator. This result can be attributed to the fact
that the coated-PE separator has a higher ionic conductivity than the
non-treated separator. The good rate capability of the cell containing γ-
Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE separator is mainly con-
sidered due to the porous structure of the coated polymer layer on the
virgin PE separator, which facilitates the migration of lithium ions
(Jeon et al., 2016).
The discharge capacity profiles of the cells assembled with the γ-
Al2O3/PVDF-HFP/TTT-coated separator and PE separator, measured
at a 0.5 C rate as a function of the cycle number, are shown in Fig. 8.
The initial discharge capacities of the cell using the prepared separators
were measured at approximately 3 m Ah. In this cycle testing, the
Fig. 6. The linear sweep voltammetry of the test cell with the prepared separators. relative discharge capacity is defined as the percent ratio of the
discharge capacity to the initial discharge capacity. As shown in
Fig. 8, the cell using the γ-Al2O3/PVDF-HFP/TTT (95/5/2)-coated
PE separator exhibited higher relative discharge capacities than that
based on the PE separator. At 100 cycles, the cells containing γ-Al2O3/
PVDF-HFP/TTT (95/5/2)-coated PE separators maintained 99% of
their initial discharge capacities but the cell using the PE separator
maintained only 88% of its initial discharge capacity. These results can
be attributed to the fact that the porous structure formed in the coated
γ-Al2O3/PVDF-HFP/TTT (95/5/2) layer increased the ionic conductiv-
ity and greatly improved the cycle stability of a lithium ion battery
(Jeon et al., 2016).

4. Conclusions

PE separators were dip-coated in the coating solution involving γ-

Al2O3/PVDF-HFP/TTT, and then dried under humidified conditions
Fig. 7. The relative discharge capacities as a function of the C-rate in cells assembled (relative Humidity 40%) followed by electron beam irradiation, where
with a PE separator, γ-Al2O3/PVDF-HFP (90/10)-coated PE separator, γ-Al2O3/PVDF-
coated-separators sealed in laminated aluminum /PE films were
HFP/TTT (90/10/2)-coated PE separator, and γ-Al2O3/PVDF-HFP/TTT (95/5/2)-
coated PE separator.
irradiated using a conventional 1 MeV electron beam accelerator at a
radiation dose of 150 kGy, at a dose rate of 10 kGy/pass at room
temperature.
Nanocomposite γ-Al2O3/PE separators were fabricated using var-
ious coating compositions. The electrolyte uptake of the nanocomposite
γ-Al2O3/PE separator was larger than that of the virgin PE separator.
In particular, the γ-Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE separa-
tor showed the highest electrolyte uptake (157%) and ionic conductiv-
ity (1.3 mS/cm). On the basis of the thermal shrinkage test, the ceramic
composite separators containing TTT irradiated by electron beam
exhibited a higher thermal resistance. Moreover, a linear sweep
voltammetry test showed that the irradiated ceramic composite se-
parators have electrochemical stabilities of up to 5.0 V. In a battery
performance test, the coin cell with γ-Al2O3/PVDF-HFP/TTT (95/5/2)-
coated PE separator had a good discharge cycle performance, in
comparison to that of a virgin PE separator.

Acknowledgement
Fig. 8. The relative discharge capacities as a function of the cycle number in the cells
assembled with PE separator and γ-Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE separa- This research was supported by Nuclear R & D program through the
tor (charge 0.5 C / discharge 0.5 C). Korea Science and Engineering Foundation funded by the Ministry of
Education, Science and Technology, Korea.
cut-off voltage of 3 V at the same current density (0.5 C rate).
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