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Crystal structure Control and Application to electrode materials of Low-expanding Composite Oxides

Research Project

Project/Area Number 07505029
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section試験
Research Field 無機工業化学
Research InstitutionTokyo Institute of Technology

Principal Investigator

WAKIHARA Masataka  Tokyo Institute of Technology, Professor, 工学部, 教授 (20016596)

Co-Investigator(Kenkyū-buntansha) SUZUKI Kimihito  Nippon Steel Co.Ltd.Investigator, 先端材料研究所, 研究員
IKUTA Hiromasa  Tokyo Institute of Technology, Research Associate, 工学部, 助手 (80242270)
UCHIDA Takashi  Tokyo Institute of Technology, Associate Professor, 工学部, 助教授 (10126310)
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1996: ¥2,200,000 (Direct Cost: ¥2,200,000)
KeywordsLithium secondary battery / Lithium manganese oxide spinel / Low-expansion / Control of crystal structure / Charge-discharge cycling / Diffusion coefficient of lithium / スピネル型酸化物正極
Research Abstract

Lithium secondary batteries using lithium-cobalt oxide, LiCoO_2 as the cathode, and carbon materials as the anode (so called "lithium ion batteries") have been commercialized, and the production is repidly expanding. However, the natural resources for cobalt is so limited (less than 9 million tons) that new cathode materials which replace cobalt are strongly expected. Manganese is one of the abundant elements, and lithium-manganese spinel oxide, LiMn_2O_4 can also successfully work as the reversible cathode of lithium secondary batteries, however, the stability of this compound in a long term charge-discarge cycling is not satisfactory when it is compared with LiCoO_2. In the present project, we have focused our efforts on the stabilization of the LiMn_2O_4 crystal lattice by substituting other metal elements for a part of manganese ion in LiMn_2O_4, i.e., LiM_yMn_<2-y>O_4. As the M elements, such metals that have stronger affinities to oxide ions compared to that of Mn-O have been chosen, e.g., Cr, Ni, Co.
Notable improvement in the charge-discharge cycling properties have been observed for LiM_yMn_<2-y>O_4. Especially, when y=1/6 and M=Co, more than 90% of the initial discharge capcity of 115 mAh/g was maintained even after 200 cycle, while in the case of LiMn_2O_4, the discharge capacity after the same cycle number was almost 60% of initial capacity. When M=Ni, although the initial capacity was not large (95mAh/g), reduction in the cycling capacity was also small. Variation of the diffusion coefficient of lithium (D_<Li>) with the lithium content x in LiM_yMn_<2-y>O_4 were also measured. It was also found by using CPR method that the D_<Li> value at x=0.5 was higher by two orders of magnitude (10^<-7.5>cm^2s^<-1>) compared with those in other x region, where lithium ions were expected to be arranged in a ordered form.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] M.Wakihara et al.: "Chemical diffusion coefficient of lithium in LiM_yMn_<2-y>O_4(M=Co and Cr)" Solid State Ionics. 86-88. 907-909 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Wakihara et al.: "Chemical diffusion coefficient of lithium in carbon fiber" J.Electrochem.Soc.143. 2606-2610 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Wakihara et al.: "Measurement of the formation enthalpy of Mo_6S_<8-y> clusrers" Thermochim.Acta. 282/283. 331-343 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 脇原將孝ら: "最新電池ハンドブック" 朝倉書店, 922 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Wakihara, Li Guohua, H.Ikuta, T.Uchida: "Chemical Diffusion Coefficients of Lithium in LiM_yMn_<2-y>O_4 (M=Co and Cr)" Solid State Ionics. 86-88. 907-909 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Uchida, Y.Morikawa, H.Ikuta, M.Wakihara: "Chemical Diffusion Coefficients of Lithium in Carbon Fiber" J.Electrochem.Soc.143. 2606-2610 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Li Guohua, K.Sakuma, H.Ikuta, T.Uchida, M.Wakihara: "Synthesis and Characterization of LiV_2O_4 as the Cathode in Secondary Lithium Batteries" Denki Kagaku. 64. 202-206 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Li Guohua, H.Ikuta, T.Uchida, M.Wakihara: "The Spinel Phases LiM_yMn_<2-y>O_4 (M=Co, Cr, Ni) as the Cathode for Rechargeable Lithium Batteries" J.Electrochem.Soc.143. 178-182 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Hinode, Y.Ohira, M.Wakihara: "Measurements of the Formation Enthalpy of Mo_6S_<8-y> Cluster" Thermochimica Acta. 282/283. 331-343 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Li Guohua, H.Ikuta, T.Uchida, M.Wakihara: "Reexamination of Copper Chevrel Phase Sulfides as Cathode in Lithium Secondary Batteries" J.Power Sources. 54. 519-521 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Miki, D.Nakazato, H.Ikuta, T.Uchida, M.Wakihara: "Amorphous MoS_2 as the Cathode in Lithium Secondary Batteries" J.Power Sources. 54. 508-510 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Hinode, T.Ohtani, M.Wakihara: "Homogeneity Range and Some Physical Properties of Intercalation Compounds of Mn_xTaS_2" J.Solid State Chem.114. 1-5 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Wakihara et al.: "Chemical diffusion coefficient of lithium in LiM_yMn_<2-y>O_4(M=Co and Cr)" Solid State Ionics. 86-88. 907-909 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Wakihara et al.: "Chemical diffusion coefficient of lithium in carbon fiber" J.Electrochem.Soc.143. 2606-2610 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Wakighara et al.: "Measurement of the formation enthalpy of Mo_6S_<8-y> clusrers" Thermochim.Acta. 282/283. 331-343 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 脇原將孝ら: "最新電池ハンドブック" 朝倉書店, 922 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Wakihara et al.: "The spinel phase Lim Mn_<2-y>O_4(M=Co,Cr,Ni)as the Cathode for Rechrgeable Lithium Cells" J.Electrochem.Soc. 143. 178-182 (1996)

    • Related Report
      1995 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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