Electrochimica Acta 57 (2011) 4045

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

A self-standing, UV-cured polymer networks-reinforced plastic crystal composite electrolyte for a lithium-ion battery
Hyo-Jeong Ha a , Yo Han Kwon b , Je Young Kim b , Sang-Young Lee a,
a b

Department of Chemical Engineering, College of Engineering, Kangwon National University, Chuncheon, Kangwondo, 200-701, Republic of Korea Batteries R&D, LG Chem, Yusong-gu, Daejon, 305-380, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
We demonstrate a facile approach to fabrication of a self-standing plastic crystal composite electrolyte for a lithium-ion battery, wherein UV (ultraviolet)-cured ethoxylated trimethylolpropane triacrylate (ETPTA) networks are incorporated into a plastic crystal electrolyte (PCE, 1 M lithium bistriuoromethanesulphonimide (LiTFSI) in succinonitrile (SN)). An ETPTA monomer having trifunctional groups is successfully crosslinked within a very short UV-exposure time of 20 s without using any solvent, leading to the formation of a self-standing, transparent, and non-sticky plastic crystal composite electrolyte (X-PCCE). Owing to the introduction of the UV-cured ETPTA networks, the X-PCCE is capable of providing unprecedentedly robust mechanical strength even at a high concentration of PCE (i.e., ETPTA/PCE = 15/85%, w/w), along with affording high ionic conductivity. In contrast, a conventional plastic crystal composite electrolyte (F-PCCE) comprising polyvinylideneuoride-co-hexauoropropylene (PVdF-HFP) and PCE is difcult to be fabricated as a self-standing lm and easily deformed by weak external stress. Notably, the X-PCCE shows signicant improvement in electrochemical stability and interfacial resistance toward lithium metal electrodes. Ionic conductivities of the X-PCCE and the F-PCCE are examined as a function of temperature and discussed under consideration of the interaction between SN, LiTFSI, and polymers in the plastic crystal composite electrolytes. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 27 November 2010 Received in revised form 24 March 2011 Accepted 24 March 2011 Available online 1 April 2011 Keywords: Lithium-ion batteries Self-standing plastic crystal composite electrolytes Succinonitrile Lithium bis-triuoromethanesulphonimide UV-curing Ethoxylated trimethylolpropane triacrylate

1. Introduction Rapidly growing demands for all-solid-state lithium-ion batteries featuring shape versatility and better safety has motivated interest in new solid electrolytes [13]. Among various solid electrolytes, polymer electrolytes consisting of solvating polymers and salt mixtures have been extensively investigated due to their superior exibility, electrolyte leakage-proof, less ammability, and low toxicity. Unfortunately, these advantages do not compensate their poor ionic conductivity. The ionic conductivity of polymer electrolytes, typically less than 104 S cm1 , is limited by chain mobility above their glass transition temperature [3]. Radically new approaches based on the concept of dissolving salts in a exible solid matrix such as a plastic crystal bearing excellent solvating capability have been suggested by several groups [48]. Plastic crystals are a kind of mesophase formed predominantly by quasi-spherical or disk-like molecules demonstrating rotational and/or orientational disorder while preserving longrange translational order [46]. This type of disorder is known to allow fast ionic mobility in a plastic crystal electrolyte [7].

Corresponding author. Tel.: +82 33 250 6338; fax: +82 33 251 3658. E-mail address: syleek@kangwon.ac.kr (S.-Y. Lee). 0013-4686/$ see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2011.03.101

Succinonitrile (SN, NCCH2 CH2 CN) is a non-ionic plastic crystalline organic molecule and shows a phase transition at around 40 C, above which the material has a plastic-crystalline phase until its melting temperature of approximately 60 C. The plasticcrystalline phase of SN can be used as a solid solvent capable of dissolving various types of lithium salts, providing high ionic conductivity of more than 103 S cm1 at room temperature [68]. Below the melting temperature of SN, SN/lithium salt electrolytes offer ionic conduction behavior predominantly in the plastic phase of SN due to the presence of trans-gauche isomerism involving rotation of molecules about central CC bonds. The trans isomer is considered an impurity phase that contributes to exacerbation of lattice defects and lowering of activation energy for ionic conduction [7]. However, SN/lithium salt-based plastic crystal electrolytes are excessively plastic and easily subjected to deformation under low stress. Therefore, they cannot be used as a self-standing solid electrolyte. Various attempts to improve the mechanical strength of SN/lithium salt-based plastic crystal electrolytes have been reported, which includes the development of composite polymeric systems involving a plastic crystal as a solid plasticizer [913]. The electrochemical and physical properties of these composite polymer electrolytes heavily depend on their composition. For instance, higher content of SN/lithium salt electrolyte is benecial in deliv-

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Fig. 1. A schematic representation of UV curing process and photographs of PCE, X-PCCE, and F-PCCE at room temperature. Chemical structures of ETPTA (UV-curable monomer), HMPP (photo-initiator), and PVdF-HFP are also illustrated.

ering high ionic conductivity but at the same time deterioration of mechanical properties appears to be unavoidable. Thus, improving both the ionic conductivity and mechanical properties of plastic crystal electrolytes presents a formidable challenge. In this study, in an endeavor to overcome the aforementioned limitations of plastic crystal electrolytes and facilitate their application to lithium-ion batteries, we develop a new self-standing plastic crystal composite electrolyte (hereinafter, abbreviated as X-PCCE), which is based on incorporation of UVcured polymer networks into a plastic crystal electrolyte (PCE, 1 M lithium bis-triuoromethanesulphonimide (LiTFSI) in SN). Ethoxylated trimethylolpropane triacrylate (ETPTA) is employed as a UV-curable monomer. ETPTA is known to be a photopolymerizable monomer under UV-exposure, affording strong mechanical strength owing to its trifunctional groups [14,15]. UV curing is a well-established, free radical photopolymerization technique that enables the facile design and control of polymer networks [1619]. Notable advantages of this UV curing process are that polymerization can be conducted without the use of a solvent and requires very short irradiation time ranging from a few seconds to a few minutes, both of which can contribute to facile preparation of crosslinked polymeric materials. In comparison to a conventional plastic crystal composite electrolyte (hereinafter, abbreviated as F-PCCE) consisting of PVdF-HFP (polyvinylideneuoride-co-hexauoropropylene) and PCE [10,11], the performance benets of the X-PCCE are elucidated in terms of mechanical properties, electrochemical stability, ionic conductivity, and interfacial resistance toward Li metal electrodes. 2. Experimental SN, LiTFSI (Li(CF3 SO2 )2 N), ETPTA (Mw = 428), and 2-hydroxy2-methyl-1-phenyl-1-propanon (HMPP) were purchased from Aldrich and PVdF-HFP (HFP content = 6 mol%) was obtained from Arkema. The chemical structures of the ETPTA (UV-curable monomer) and HMPP (photo-initiator) are displayed in Fig. 1. As

the rst step, PCE (i.e. 1 M LiTFSI in SN) was prepared by adding a predetermined amount of LiTFSI into SN melted at 60 C in an argon-lled glove box. For the fabrication of the X-PCCE, the PCE was mixed with the ETPTA and HMPP. The weight-based composition of (ETPTA:HMPP)/PCE was xed at 15/85, where the concentration of the HMPP was xed at 1 wt% of the ETPTA. The mixture solution was cast onto a polypropylene (PP) sheet and then exposed to UV-irradiation for 20 s, leading to facile fabrication of a self-standing, transparent, and non-sticky plastic crystal composite electrolyte incorporating crosslinked ETPTA networks. UV curing was performed using a Hg UV lamp (100 W, Lichtzen), with a radiation peak intensity of approximately 2000 mW cm2 on the surface of samples. The thickness of the X-PCCE was observed to be around 200 m. A schematic representation of the UV curing process and the physical appearance of the samples are given in Fig. 1. Meanwhile, the F-PCCE was prepared via a conventional solution-casting technique [913]. The weight-based composition of the F-PCCE was identical to that of the X-PCCE, i.e. PVdF-HFP/PCE = 15/85. Predetermined amounts of PVdF-HFP and PCE were dissolved into anhydrous acetone and the solutions were then vigorously mixed until the mixture appeared to be homogeneous. The mixture was cast onto a PP sheet, followed by evaporation of the solvent in an argon-lled glove box for 1 day. The sample was further dried under vacuum at 30 C for 2 days. The thickness of the F-PCCE was measured to be approximately 200 m. The UV curing reaction and specic interaction between components of the plastic crystal composite electrolytes were examined using a FT-IR spectrometer (FT-3000, Excalibur) with a spectral resolution of 4 cm1 . The gel content of the X-PCCE was determined by measuring the weight loss of the samples after being subjected to solvent extraction in dimethyl carbonate (DMC) at 70 C for 8 h and subsequently in acetone at room temperature for 24 h. The mechanical properties of the plastic crystal composite electrolytes were measured from stressstrain curves using a tensile tester (AG-2000A, Shimadzu) at a strain rate of 50 mm min1 . The ionic conductivity of the plastic crystal composite electrolytes

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was obtained by an AC impedance analysis using a VSP classic (Bio-Logic) over a frequency range of 1106 Hz over a temperature range of 3060 C. The electrochemical stability window of the plastic crystal composite electrolytes was evaluated by linear sweep voltammetry performed on a working electrode of stainlesssteel and a counter and reference electrode of lithium-metal at a scan rate of 1.0 mV s1 . The interfacial stability of the plastic crystal composite electrolytes toward Li metal electrodes was examined by measuring the time evolution of AC impedance spectra of a symmetrical cell (Li metal/plastic crystal composite electrolyte/Li metal) at room temperature. The thermal characteristics of the plastic crystal composite electrolytes, particularly focusing on the Tcp (transition temperature from normal crystal to plastic crystal phase) and Tm (melting peak temperature) of SN, were examined by differential scanning calorimetry (DSC, DuPont Q2000) at a heating rate of 10 C min1 . 3. Results and discussion

0.16 0.14 0.12 X-PCCE F-PCCE

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The physical appearance of the PCE (=1 M LiTFSI in SN), XPCCE, and F-PCCE at room temperature is depicted in Fig. 1. Whereas the PCE shows liquid-like behavior, both plastic crystal composite electrolytes (X-PCCE and F-PCCE) present a solidied gel-like appearance. An interesting nding is that the X-PCCE incorporating the UV-cured ETPTA networks shows unprecedentedly robust mechanical strength, even at a high concentration of PCE (ETPTA/PCE = 15/85%, w/w). The X-PCCE is self-standing, highly rigid, and shows strong resistance to breakage upon appreciable bending or stretching. In contrast, the F-PCCE comprising PVdFHFP and PCE is difcult to be fabricated as a self-standing lm. The F-PCCE is mechanically very weak and easily deformed by weak external stress, which corresponds well with the results reported in the previous studies [10,11].

This remarkable improvement in the mechanical strength of the X-PCCE is further conrmed by comparing the tensile properties of the plastic crystal composite electrolytes (Fig. 2). The X-PCCE shows tensile strength (0.13 MPa) nearly 3 times higher than that (0.04 MPa) of the F-PCCE. This discloses that the incorporation of crosslinked ETPTA networks effectively improves the mechanical properties of the PCE. The present work is, to the best of our knowledge, the rst report of a self-standing plastic crystal composite electrolyte that employs the UV-cured polymer networks. To dates, previous studies on enhancement of the mechanical properties of plastic crystal electrolytes have been limited to the addition of linear polymers such as PEO (polyethylene oxide) [9,10], PVdF-

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Fig. 4. DSC proles demonstrating transition temperatures (Tcp and Tm ) of SN in: (a) pristine SN, (b) PCE, (c) F-PCCE, and (d) X-PCCE.

Fig. 5. Linear sweep voltammograms of (a) X-PCCE and (b) F-PCCE on a working electrode of stainless-steel and a counter and reference electrode of lithium-metal at a scan rate of 1.0 mV s1 .

HFP [10,11], and PAN (polyacrylonitrile) [12,13]. These approaches often fail to achieve satisfactory mechanical strength and this shortcoming becomes more pronounced at high concentrations of plastic crystal electrolytes. The crosslinking reaction in the X-PCCE was examined by observing the characteristic FT-IR peaks assigned to acrylic C C bonds (16101625 cm1 ) of the ETPTA monomer before/after the UV-irradiation. Fig. 3 shows that after the UV-irradiation, the FT-IR peaks of the C C bonds disappear, thus verifying that the ETPTA monomer is successfully photo-polymerized. This UV curing reaction was further conrmed by measuring the gel content of the X-PCCE. The gel content (i.e., insoluble fraction after being subjected to solvent (DMC and acetone) extraction) of the X-PCCE was observed to be 99.3%, which indicates that the crosslinking of ETPTA monomer is almost entirely completed after the UV-irradiation. The plastic crystal behavior of the X-PCCE and the F-PCCE was investigated by characterizing the thermal behavior of SN in the plastic crystal composite electrolytes, wherein the DSC scans were implemented in the heating mode. Fig. 4 shows that for the pristine SN (Fig. 4(a)), two endothermic peaks assigned to Tcp and Tm are observed at 39 C and 58 C, respectively. Consistent with the results of previous publications [68], the addition of LiTFSI into SN leads to a large reduction in Tm (58 C 12 C) and an insignificant change in Tcp of SN (Fig. 4(b)). This reects an increase in the concentration of structural defects (i.e., trans isomers) of SN. It is apparent that the X-PCCE as well as the F-PCCE demonstrates plastic crystal behavior. While the F-PCCE (Fig. 4(c)) shows Tcp of 40 C and Tm of 2 C, the X-PCCE (Fig. 4(d)) presents characteristic peaks of SN at 39 C (Tcp ) and 20 C (Tm ). More detailed investigation of the transition temperatures of the SN in the X-PCCE and F-PCCE was carried out in the following sections, and the results are discussed in terms of the interaction between SN, LiTFSI, and polymers in the plastic crystal composite electrolytes. The electrochemical stability window of the plastic crystal composite electrolytes was observed from linear sweep voltammograms (Fig. 5). In comparison to the F-PCCE, the X-PCCE shows improved anodic stability and no decomposition of any components takes place below 5.0 V vs. Li+ /Li. This demonstrates that the X-PCCE could be a promising solid electrolyte in high-voltage lithium-ion batteries. The time evolution in interfacial resistance of the plastic crystal composite electrolytes toward Li metal electrodes was examined by measuring the electrochemical impedance spectra of the symmetrical cell (Li metal/plastic crystal composite electrolyte/Li metal)

at room temperature. The real part of the impedance at the highest frequency signies the bulk resistance of an electrolyte, and the amplitude of a semicircle is representative of the interfacial resistance between the electrodes and electrolytes [1619]. It is generally observed that after continuous increase of impedance due to the growth of passive layers formed on electrodes during the initial stage, the resistive layers are stabilized, giving a lower or constant interfacial resistance value [17,18]. Fig. 6 shows that for both the X-PCCE and F-PCCE, the interfacial resistance of the cells increases with time, which reects continuous growth of a passive layer on the surface of the Li metal electrodes. It is of interest that the X-PCCE shows different behavior of interfacial resistance from the F-PCCE. Initially, the interfacial resistance of the X-PCCE increases to about 700 after 3 days, but then reduces with time and nally stabilizes to a value below 300 after 22 days (Fig. 6(a)). In contrast, the interfacial resistance of the F-PCCE continues to increase with time and stabilizes at about 900 after 10 days (Fig. 6(b)), wherein another increase of Z with time at low frequency region may indicate appearance of a semicircle related to an additional relaxation phenomenon, which will be further investigated in subsequent studies. The suppressed growth in the interfacial resistance indicates that the X-PCCE offers better compatibility toward Li metal electrodes, in comparison to the F-PCCE. The temperature-dependent ionic conductivity of the X-PCCE is compared with that of the F-PCCE. Fig. 7 exhibits that owing to the high concentration of PCE in the plastic crystal composite electrolytes (polymer/PCE = 15/85%, w/w), both the X-PCCE and the F-PCCE present satisfactory ionic conductivities of more than 103 S cm1 at room temperature, although this value is marginally lower than that of the PCE itself. A notable achievement in the X-PCCE, as compared to the F-PCCE, is the realization of strong mechanical strength, while simultaneously affording high ionic conductivity. Over a wide range of temperatures, the ionic conductivity of the X-PCCE is slightly lower than that of the F-PCCE. This difference in the ionic conductivity between the X-PCCE and the F-PCCE can be analyzed in the context of the interaction between SN, LiTFSI, and polymers in the plastic crystal composite electrolytes. Fig. 8(a) shows that the characteristic FT-IR peaks assigned to C N bonds of SN are observed at 2254.9 cm1 (X-PCCE), 2254.0 cm1 (X-PCCE without LiTFSI, i.e. UV-cured ETPTA networks/SN), 2256.0 cm1 (FPCCE), and 2254.0 cm1 (F-PCCE without LiTFSI, i.e. PVdF-HFP/SN), respectively. The differences ( ) in the peaks of the C N bonds are measured to be 0.9 cm1 (= (X-PCCE) (X-PCCE without LiTFSI))

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and 2.0 cm1 (= (F-PCCE) (F-PCCE without LiTFSI)). This indicates that in comparison to the SN in the X-PCCE, the SN in the F-PCCE is strongly affected by the incorporation of LiTFSI. In addition to this FT-IR characterization, a DSC analysis, focusing on the Tm of SN in the samples, was carried out to further examine the interaction between the components of the plastic crystal composite electrolytes. It is known that the shift in the Tm of SN in plastic crystal electrolytes heavily depends on the interaction of SN with LiTFSI [1013]. Fig. 8(b) exhibits that with addition
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of LiTFSI into the polymer/SN mixtures, the Tm of SN shifts to a lower temperature, revealing deterioration in the crystalline structure of SN. Interestingly, relative to the SN in the X-PCCE, the larger shift in the Tm of SN is observed in the F-PCCE. The differences in the Tm (= Tm ) of SN between the samples are 31 C (=Tm (X-PCCE without LiTFSI) Tm (X-PCCE)) and 54 C (=Tm (F-PCCE without LiTFSI) Tm (F-PCCE)), respectively. Along with the FT-IR characterization, this DSC analysis conrms that the SN in the F-PCCE is heavily inuenced by the LiTFSI. In other words, the relatively stronger interaction between the SN and the LiTFSI could be expected in the F-PCCE, in comparison to the X-PCCE. This may possibly contribute to facile dissociation of LiTFSI and an increase in the lattice defects of SN. High dissociation of LiTFSI is expected to offer large number of lithium ions [11,12]. Deterioration of crystalline structure of SN is known to enhance the rate of isomer transition from gauche to trans, which consequently increases the trans conformer concentration [68]. The trans phase, i.e. a high defect density state phase, facilitates ionic mobility in SN-based plastic crystal electrolytes. Another feasible explanation on the ionic mobility of the F-PCCE and X-PCCE is that the ETPTA polymer network may have a stronger interaction with the lithium ions than the PVdF-HFP due to the presence of nine oxygen atoms in each ETPTA molecule, which thus may lead to a decrease in lithium ion mobility. In summary, the facile ionic mobility as well as favorable dissociation of LiTFSI may explain the slightly high ionic conductivity in the F-PCCE. By exploiting the aforementioned understanding of the interaction between SN, LiTFSI, and polymers in the plastic crystal composite electrolytes, we will attempt to further improve the ionic conductivity of the X-PCCE in future studies.

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and the gel content of the X-PCCE. The highly crosslinked ETPTA networks played a key role in endowing the X-PCCE with greater mechanical strength, while simultaneously delivering high ionic conductivity. Moreover, the X-PCCE presented superior anodic stability and suppressed growth of interfacial resistance toward Li metal electrodes, in comparison to the F-PCCE comprising PVdF-HFP and PCE. Meanwhile, when LiTFSI is incorporated into polymer/SN mixtures, a relatively small shift in the characteristic FT-IR peaks (C N bonds) and Tm of SN was observed in the X-PCCE, indicating that the SN is weakly affected by the LiTFSI. This may contribute to relatively poor dissociation of LiTFSI and sluggish ionic movement in the X-PCCE, which would results in slightly low ionic conductivity, as compared to the F-PCCE. Our future studies will focus on further improvement of the ionic conductivity of the XPCCE and characterization of the electrochemical performances of cells assembled with the X-PCCE. Acknowledgment This research was supported by the Converging Research Center Program through the Ministry of Education, Science and Technology (2010K001090). References
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Fig. 8. Characterization of interaction between SN, LiTFSI, and polymers in X-PCCE and F-PCCE: (a) FT-IR spectra (C N bonds) of SN and (b) DSC proles (Tm ) of SN.

4. Conclusion We developed a new self-standing plastic crystal composite electrolyte (X-PCCE) for a lithium-ion battery, which is based on incorporation of UV-cured ETPTA networks into a PCE (=1 M LiTFSI in SN). Successful crosslinking of the ETPTA networks was veried by analyzing the characteristic FT-IR peaks of acrylic C C bonds

[16] [17] [18] [19]