• Proceedings of the KIEE Conference
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• 1994.07b
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• pp.1229-1232
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• 1994

The purpose of this study is to research and develop solid polymer electrolyte(SPE) for Li secondary battery. This paper describes the effects of lithium salts, plasticizer addition and temperature dependence of conductivity of PEO electrolytes. Polyethylene oxide(PEO) based polymer electrolyte films were prepared by solution casting an acetonitrile solution of preweighed PEO and Li salt. After solvent evaporation, the electrolyte films were vacuum-dried at $60^{\circ}C$ for 48h, the thickness of the films were $90{\sim}110{\mu}m$. The conductivity properties of prepared PEO electrolytes are summarized as follows. PEO electrolyte complexed with $LiClO_4$ shows the better conductivity of the others. $PEO-LiClO_4$ electrolyte when $EO/Li^+$ ratio is 8, showed the best conductivity. Optimum operating temperature of PEO electrolyte is $60^{\circ}C$. By adding propylene carbonate and ethylene carbonate to $PEO-LiClO_4$ electrolyte, its conductivity was higher than $PEO-LiClO_4$ without those. Also $PEO_8LiClO_4$ electrolyte remains static up to 4.5V vs. $Li/Li^+$.

• Bulletin of the Korean Chemical Society
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• v.33 no.9
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• pp.2949-2954
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• 2012

Nano ZnO with an average size of 8 nm was prepared by thermal decomposition of zinc oxalate at $450^{\circ}C$. A series of based composite polymer electrolyte PEO-$LiClO_4$ and nano ZnO as a filler have been synthesized using solution cast technique, with varying the filler ratio systematically. XRD, DSC and FTIR studies have been conducted to investigate the structure and interaction of different groups in the composite polymer electrolyte. Effect of nano ZnO ceramic filler concentration on the structure of composites and their electrical properties (DC-conductivity, AC-conductivity, dielectric constant, dielectric loss and impedance) at different frequencies and temperatures was studied. Melting temperature ($T_m$) of PEO decreased with the addition of both $LiClO_4$ salt and nano ZnO filler due to increasing the amorphous state of polymer. All composite samples showed an ionic conductivity. The maximum room temperature ionic conductivity is found for $(ZnO)_{0.5}(PEO)_{12}(LiClO_4)$ composite sample. All the results are correlated and discussed.

• Applied Chemistry for Engineering
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• v.7 no.3
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• pp.433-442
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• 1996

Electrochemical characteristics and physical properties of polymer electrolyte which immobilized lithium salts such as $LiClO_4$ and $LiCF_3SO_3$ and plasticizers such as ethylene carbonate(EC) and propylene carbonate(PC) in high molecular weight poly(ethylene oxide)[PEO] polymer was investigated. PEO-Li based polymer electrolyte with plasticizers showed ionic conductivity of $10^{-4}S/cm$ at room temperature and high electrochemical stability up to 4.5 V(vs. $Li^+/Li$), so it can be applied to lithium secondary battery. The crystallinity of PEO decreased with the addition of lithium salts and plasticizers, especially $LiClO_4$ and PC showed more effective than and $LiCF_3SO_3$ and EC. Glass transition temperature($T_g$) of polymer electrolyte increased with increasing lithium salt concentration whereas melting temperature ($T_m$) decreased. Polymer electrolyte with plasticizers crystallized at $6^{\circ}C$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1994.11a
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• pp.82-85
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• 1994

The purpose of this study is to research and develop solid polymer electrolyte(SPE) for Li secondary battery. This paper describes effects of plasticizer addition and temperature dependence of conductivity of these PEO electrolytes. Adding propylene carbonate and ethylene carbonate to PEO-LiClO$_4$electrolyte, its conductivity was higher than PEO-LiClO$_4$ itself. Steady state current method and AC impedance used for the determination of transference number in PEO electrolyte film. The transference number of PEO$\_$8/LiClO$_4$PC$\_$5/EC$\_$5/ polymer electrolyte film is 0.45 at 60$^{\circ}C$.

• Polymer(Korea)
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• v.31 no.3
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• pp.263-268
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• 2007

Most of current works on the PEO-salt electrolytes has been focused on the enhancement of ionic conductivity with an addition of nano-ceramic fillers, but the significant drop of the conductivity with storage time is still in question and has been frequently overlooked. The conductivity drop with aging time has been assumed to come from the incorporation of ceramic particles. However, according to authors, the reported high-temperature values of the conductivity of pure $PEO_8LiCIO_4$ electrolytes are nearly in agreements, but the low temperature values are in great discrepancy reaching up to 10000 times. It indicates that the conductivity at ambient temperature is greatly dependent on the thermal history and sample preparations. In this paper, we showed that the ionic conductivities of both $PEO_8LiCIO_4$ and $PEO_8LiClO_4/Al_2O_3$ polymer electrolytes are strongly dependent on the thermal pretreatment and aging time. The conductivity drop with aging time of both ceramic-free and ceramic composite electrolytes has been measured to be nearly parallel. We showed that the conductivity relaxation with aging time is inherent irrespective of the incorporation of nano-ceramic fillers, since the PEO electrolytes at ambient temperature are in two-phase nature being in non-equilibrium state, never reaching completion.

• Polymer(Korea)
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• v.27 no.3
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• pp.265-270
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• 2003

In spite of high ionic conductivity, the polymer gels have poor mechanical properties and high reactivity with lithium metal anode. To solve these problems, the dry solid systems and polymer composites have been intensively studied, due to their good mechanical, thermal, chemical, and electrochemical stability. The objectives of this experiment were to improve ionic conductivity and mechanical properties of the solid polymer electrolytes based on PEO-LiClO$_4$. To obtain higher ionic conductivity and better mechanical properties, ceramic or rubber phase was added in the PEO-LiClO$_4$(8:1) matrix. The results showed that ionic conductivity and mechanical properties were improved. The ionic conductivity of the samples was as high as 10$\^$-5/ S cm$\^$-1/. This value is similar to the best ionic conductivity ever reported in the solid drying system. To obtain better results, we used PEO with various molecular weights (600∼8000) and changed the salt contents. By using DSC, we found that the addition of salt reduced the crystallinity of PEO. The mobility of polymer dependence on salt contents was examined by FT-IR.

• Elastomers and Composites
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• v.39 no.1
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• pp.36-41
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• 2004

Solid polymer electrolytes were prepared by UV irradiation of the blends consisting of poly(ethylene oxide)(PEO), epoxy diacrylate(EDA) and LiClO_4$. Conductivities of the electrolyte films were measured as a function or blend composition, salt concentration and temperature. The electrolyte having the composition of poly(ethylene oxide) (70% by weight)/epoxy diacrylate (30% by weight) with mole ratio of 10 of ethylene $oxide/Li^+$ exhibited a high ionic conductivity of $1.2{\times}10^{-5} S/cm$ at $25^{\circ}C$. This blend is transparent and shows elastomeric properties. Morphological studies by means of differential scanning calorimetry, X-ray diffraction and polarized optical microscopy indicated that the cured epoxy chains in the blends inhibit the crystallization of poly (ethylene oxide) and thereby induce the blend systems to be completely amorphous in certain compositions.

• Polymer(Korea)
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• v.28 no.6
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• pp.455-459
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• 2004

Ionic conductivities of poly(ethylene oxide) (PEO)-based electrolytes are in a considerable inconsistency in many papers, varying more than three orders of magnitude for just same compositions. In PEO-salt-ceramic composite electrolytes, it has been also reported that the conductivity can be variant by almost three orders of magnitude according to thermal treatment and it has been regarded as a consequence of polymer-ceramic particle interaction. In this paper, we present a more systematic study on the change of ionic conductivity for ceramic-free PEO$_{10}$LiClO$_4$ polymer electrolytes, and found that the ionic conductivity can be variant more than hundred times according to thermal history. The slow recrystallization kinetics of PEO polymer is discussed to be responsible for the thermal history effect. Present results reveal that the effect of ceramic filler is not a main cause of the conductivity relaxation phenomenon.n.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1996.11a
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• pp.109-112
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• 1996

The purpose of this study is to research and develop solid polymer electrolyte(SPE) for all-stolid-state lithium battery. We investigated conductivity, electrochemical properites and impedence spectroscopy of poly(ethylene oxide)[PEO]/poly(vinylidene fluoride)[PVOF] blend electrolytes and charge/discharge cycling of LiCoO$_2$/SPE/Li cell. By adding PVDF and plasticizer to PEO-LICIO$_4$electrolyte, its condustivity was higher than that of PEO-LiCIO$_4$electrolyte. Also PEO$_4$PVDF$_4$LiClO$_4$PC$_{5}$EC$_{5}$ remains stable up to 4.4V vs Li/Li. The discharge capacity of the LiCoO$_2$composite cathode was 92mAh/g based on LiCoO$_2$.EX>.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.11 no.9
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• pp.733-738
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• 1998

본 논문에서는 고체 리듐 전지를 개발하기 위하여 poly(ethylene oxide) [PEO] 에 $LiClO_4$, poly (vinylidene fluoride) [PVDF] 및 가소제로 propylene carbonate [PC] 와 ethylene carbonate[EC] 등을 혼합여 고분자 저해질을 제조하였다. 또한 고체 리듐 전지용 정극으로써 우수한 특성이 기대되는 $Li_xV_3O_8$을 졸-겔법에 의해 합성하여 $Li_xV_3O_8$SPE/Li cell 의 전기화학적 특성을 측정하였다. 고분자 matrix는 PEO와 PVDE를 혼합 사용한 결과 $PEO_4 PVDF_4LiCIO_4PC_5EC_5$ 고분자 전해질이 상온에서 $5.2 {\times} 10{-3}$ S/cm 의 높은 이온 전도도를 나타냈으며 리듐 이온 transference number는 0.3이었다. 졸-겔법에 의해 제조된 $Li_xV_3O_8$을 사용한 $Li_xV_3O_8$SPE/Li cell의 방전시 cell 저항이 방전 초기에는 비소한 증가를 하다가 방전 말기 전압인 2.0V에서 크게 증가하였다. $Li_xV_3O_8$ composite 정극의 첫 번째 방전 용량은 295㎃h/g이었으며 8번째 충방전 싸이클부터 방전 용량이 안정화 되었고 15번째 방전 용량도 212㎃h/g으로 고체 전지용 정극으로써 우수한 특성을 보였다.