• Title/Summary/Keyword: Lithium ionic conductivity

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Electrochemical Properties of 1,1-Dialkyl-2,5-bis(trimethylsilylethynyl)siloles as Anode Active Material and Solid-state Electrolyte for Lithium-ion Batteries

  • Hyeong Rok Si;Young Tae Park
    • Journal of the Korean Chemical Society
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    • v.67 no.6
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    • pp.429-440
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    • 2023
  • 1,1-Dialkyl-2,5-bis(trimethylsilylethynyl)-3,4-diphenylsiloles (R=Et, i-Pr, n-Hex; 3a-c) were prepared and utilized as anode active materials for lithium-ion batteries; 3a was also used as a filler for the solid-state electrolytes (SSE). Siloles 3a-c were prepared by substitution reactions in which the two bromine groups of 1,1-dialkyl-2,5-dibromo-3,4-diphe- nylsiloles, used as precursors, were substituted with trimethylsilylacetylene in the presence of palladium chloride, copper iodide, and triphenylphosphine in diisopropylamine. Among siloles 3a-c, 3a had the best electrochemical properties as an anode material for lithium-ion batteries, including an initial capacity of 758 mAhg-1 (0.1 A/g), which was reduced to 547 mAhg-1 and then increased to 1,225 mAhg-1 at 500 cycles. A 3a-composite polymer electrolyte (3a-CPE) was prepared using silole 3a as an additive at concentrations of 1, 2, 3, and 4 wt.%. The 2 wt.% 3a-CPE composite afforded an excellent ionic conductivity of 1.09 × 10-3 Scm-1 at 60℃, indicating that silole 3a has potential applicability as an anode active material for lithium-ion batteries, and can also be used as an additive for the SSE of lithium-ion batteries.

Synthesis And Ionic Conductivity of Siloxane Based Polymer Electrolytes with Propyl Butyrate Pendant Groups

  • Jalagonia, Natia;Tatrishvili, Tamara;Markarashvili, Eliza;Aneli, Jimsher;Grazulevicius, Jouzas Vidas;Mukbaniani, Omar
    • Korean Chemical Engineering Research
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    • v.54 no.1
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    • pp.36-43
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    • 2016
  • Hydrosilylation reactions of 2.4.6.8-tetrahydro-2.4.6.8-tetramethylcyclotetrasiloxane with allyl butyrate catalyzed by Karstedt's, $H_2PtCl_6$ and Pt/C catalyst were studied and 2.4.6.8-tetra (propyl butyrate)-2.4.6.8-tetramethylcyclotetrasiloxane was obtained. The reaction order, activation energies and rate constants were determined. Ringopening polymerization of 2.4.6.8-tetra (propyl butyrate)-2.4.6.8-tetramethylcyclotetrasiloxane in the presence of $CaF_2$, LiF, KF and anhydrous potassium hydroxide in $60-70^{\circ}C$ temperature range was carried out and methylsiloxane oligomers with regular arrangement of propyl butyrate pendant groups were obtained. The synthesized products were studied by FTIR and NMR spectroscopy. The polysiloxanes were characterized by wide-angle X-ray, gel-permeation chromatography and DSC analyses. Via sol-gel processes of oligomers doped with lithium trifluoromethylsulfonate or lithium bis (trifluoromethylsulfonyl)imide, solid polymer electrolyte membranes were obtained. The dependences of ionic conductivity of obtained polyelectrolytes on temperature and salt concentration were investigated, and it was shown that electric conductivity of the polymer electrolyte membranes at room temperature changed in the range $3.5{\times}10^{-4}{\sim}6.4{\times}10^{-7}S/cm$.

Electrochemical Characteristics of Microporous Polymer Electrolytes Based on Poly(vinylidene-co-hexafluoropropylene) (PVdF계 미세기공 고분자 전해질의 전기화학적 특성)

  • Jung Kang-Kook;Kim Jong-Uk;Ahn Jou-Hyeon;Kim Ki-Won;Ahn Hyo-Jun
    • Journal of the Korean Electrochemical Society
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    • v.7 no.4
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    • pp.183-188
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    • 2004
  • In order to develop polymer electrolyte for lithium/sulfur batteries, highly microporous P(VdF-HFP) membranes were prepared by phase inversion method. Porous structure was controlled by extracting NMP with mixture of deionized water and methanol. Porous structure of the membranes was observed with SEM. Polymer electrolytes were prepared by soaking the porous membranes in 1M $LiCF_3SO_3-TEGDME/EC$. The ionic conductivity of polymer electrolyte was found to be at high as $2\times10^{-3}S/cm$ when the polymer membrane extracted by $80\%$ methanol was used. The microporous polymer electrolyte optimized in this work displayed high ionic conductivity, uniform pore size, low interfacial resistance and stable ionic conductivity with storage time. The ionic conductivity of polymer electrolytes was measured with various lithium salts, and the conductivity showed $3.3\times10^{-3}S/cm$ at room temperature when $LiPF_6$ was used as a lithium salt.

Electrochemical properties of PEO-based solid polymer electrolytes blended with different room temperature ionic liquids

  • Kim, Y.H.;Cheruvally, G.;Choi, J.W.;Ahn, J.H.;Kim, K.W.;Ahn, H.J.;Song, C.E.;Choi, D.S.
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.276-276
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    • 2006
  • The incorporation of room temperature ionic liquids (IL) in poly (ethyleneoxide)-lithium salt (PEO-LiX) based solid polymer electrolytes is presently being studied as an effective means of enhancing the room temperature ionic conductivity of these electrolytes to acceptable levels for use in lithium batteries. In the present study, $PEO_{20}-LiTFSI$ solid polymer electrolyte was blended with three different ionic liquids, namely 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMIMTFSI), 1-butyl-3-methylimidazolium tetraflouroborate (BMIMBF4) and 1-butyl-3-methylimidazolium trifluromethanesulfonate ($BMIMCF_{3}SO_{3}$). The incorporation of all these ILs resulted in the enhancement of ionic conductivity, the effect being more pronounced at lower temperatures. Electrochemical properties of the blended electrolytes were studied by cyclic voltammetry, linear sweep voltammetry and interfacial resistance measurements. The optimum results were obtained with the blending of BMIMTFSI in the solid polymer electrolyte.

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Effect of Lithium Ion Concentration on Electrochemical Properties of BF3LiMA-based Self-doping Gel Polymer Electrolytes (BF3LiMA기반 자기-도핑형 겔 고분자 전해질의 전기화학적 특성에 미치는 리튬이온 농도의 영향)

  • Kang, Wan-Chul;Ryu, Sang-Woog
    • Journal of the Korean Electrochemical Society
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    • v.13 no.3
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    • pp.211-216
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    • 2010
  • Boron trifluoride lithium methacrylate ($BF_3$LiMA)-based gel polymer electrolytes (GPEs) were synthesized with various $BF_3$LiMA concentration to elucidate the effect on ionic conductivity and electrochemical stability by a AC impedance and linear sweep voltammetry (LSV). As a result, the highest ionic conductivity reached $5.3{\times}10^{-4}Scm^{-1}$ at $25^{\circ}C$ was obtained for 4 wt% of $BF_3$LiMA. Furthermore, high electrochemical stability up to 4.3 V of the $BF_3$LiMA-based GPE was observed in LSV measurement since the counter anion was immobilized in this self-doped system. On the other hand, it was assumed that there was a rapid decomposition of electrolytes on a lithium metal electrode which results in a high solid electrolyte interface (SEI) resistance. However, a high stability toward graphite or lithium cobalt oxide (LCO) electrode thereby a low SEI resistance was observed from the AC impedance measurement as a function of storage time at $25^{\circ}C$. Consequently, the high ionic conductivity, good electrochemical stability and the good interfacial compatibility with graphite and LCO were achieved in $BF_3$LiMA-based GPE.

The Effect of Inorganic Material in Polymer Electrolyte for Lithium Secondary Battery (리튬이차전지용 고분전해질의 무기물의 첨가에 대한 영향)

  • Park, Soo-Gil;Park, Jong-Eun;Lee, Hong-Ki;Lee, Ju-Seong
    • Proceedings of the KIEE Conference
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    • 1998.11c
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    • pp.822-824
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    • 1998
  • The lithium polymer battery with polymer electrolyte is expected as a safe and long cycle life battery. This paper reports primarily the recent development results of a solid polymer electrolyte, which is a key point of the secondary battery system. The new type of polymer electrolyte was prepared under a dry Ar atmosphere by dissolving $LiCIO_4$ in a matrix of EC, PC and then dispersing polyacrylonitrile(PAN). Also adding some inorganic filler $Al_2O_3$. The dispersed solution heated at $120^{\circ}C$. The polymer electrolyte were characterized by EIS(Electrochemical Impedance Spectroscopy), TGA(Thermo Gravimetric analysis), DMA(Dynamic Mechanical Analyzer), DSC (Differential Scanning Calorimetry). The lithium ion yield is 0.29 when PAN-$Al_2O_3$ which was applied DC 5mV. The ionic conductivity of PAN, PAN-$Al_2O_3$ polymer electrolytes were showed $1.0{\times}10^{-4}S/cm$, $8.4{\times}10^{-4}S/cm$ at room temperature. When inorganic filler was added in the polymer electrolyte, ionic conductivity and lithium yield more larger than without inorganic filler.

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Lithium Transition Metal Phosphate Cathodes for Advanced Lithium Batteries (리튬이온전지에서 새로운 양극재료를 위한 금속인산화물)

  • ;Yet Ming Chiang
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2003.11a
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    • pp.26-26
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    • 2003
  • Lithium storage electrodes for rechargeable batteries require mixed electronic-ionic conduction at the particle scale in order to deliver desired energy density and power density characteristics at the device level. Recently, lithium transition metal phosphates of olivine and Nasicon structure type have become of great interest as storage cathodes for rechargeable lithium batteries due to their high energy density, low raw materials cost, environmental friendliness, and safety. However, the transport properties of this family of compounds, and especially the electronic conductivity, have not generally been adequate for practical applications. Recent work in the model olivine LiFePO$_4$, showed that control of cation stoichiometry and aliovalent doping results in electronic conductivity exceeding 10$^{-2}$ S/cm, in contrast to ~10$^{-9}$ S/cm for high purity undoped LiFePO$_4$. The increase in conductivity combined with particle size refinement upon doping allows current rates of >6 A/g to be utilized while retaining a majority of the ion storage capacity. These properties are of much practical interest for high power applications such as hybrid electric vehicles. The defect mechanism controlling electronic conductivity, and understanding of the microscopic mechanism of lithiation and delithiation obtained from combined electrochemical and microanalytical techniques, will be discussed

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Synthesis and Characterization of Quaternary Ammonium-based Ionic Liquids Containing an Alkyl Carbonate Group

  • Nguyen, Dinh Quan;Oh, Ji-Hee;Kim, Chang-Soo;Kim, Seung-Wook;Kim, Hong-Gon;Lee, Hyun-Joo;Kim, Hoon-Sik
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2299-2302
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    • 2007
  • A series of quaternary ammonium-based ionic liquids (ILs) containing an alkyl carbonate group on the cation was first prepared and their physical and electrochemical properties including density, viscosity, thermal stability, electrochemical stability, and ionic conductivity were reported. These ILs exhibited wide electrochemical windows of at least 5.0 V and relatively high conductivities. In contrast to dialkyl-substituted ionic liquids, the ILs with an alkyl carbonate group on the cation showed much smaller drop in conductivities when mixed with a lithium salt, due to the interaction of lithium ions with carbonate groups. Upon interaction with a Li salt, the carbonyl stretching frequency of the carbonate group shifted to a lower frequency whereas the peak associated with C-O single bond moved to a higher frequency.