Understanding irreversible capacity in LixNi1-yFeyO2 cathode materials

被引:86
作者
Mueller-Neuhaus, JR [1 ]
Dunlap, RA
Dahn, JR
机构
[1] Dalhousie Univ, Dept Phys, Halifax, NS B3H 3J5, Canada
[2] Dalhousie Univ, Dept Chem, Halifax, NS B3H 3J5, Canada
关键词
D O I
10.1149/1.1393945
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
A study was made of LixNi1-yFeyO2 lithium-ion cell cathode materials. Through a series of experiments including cyclic voltammetry, X-ray diffractometry, Mossbauer spectroscopy, in situ X-my diffractometry, and in situ Mossbauer spectroscopy, it was determined that the phenomenon commonly referred to as "irreversible capacity" in LixNi1-yFeyO2 lithium-ion cell cathode materials is a misnomer. Cells utilizing LixNi1-yFeyO2 with 0.05 less than or equal to y less than or equal to 0.10 as the cathode active material(vs. a lithium metal anode) have been reversibly cycled between 0.64 less than or equal to x less than or equal to 1.00 (100 mAh/g). The recovery of the "irreversible capacity" involved a discharge through a similar to 2 V plateau during which it is believed that a surface layer of Li>1Ni1-yFeyO2 is present. Also, a new transition has been observed between two O3 phases (belonging to the space group R (3) over bar m) during charge beginning at the start of charge and reaching completion by x approximate to 0.82 (50 mAh/g). The cause of this transition as well as the formation of thr Li>1Ni1-yFeyO2 surface layer during discharge are explained in terms of the mobility of lithium ions in die intercalation host being related to the availability of monovacancy and divacancy hopping paths. (C) 2000 The Electrochemical Society. S0013-4651(00)02-093-0. All rights reserved.
引用
收藏
页码:3598 / 3605
页数:8
相关论文
共 17 条
  • [1] Reversibility of LiNiO2 cathode
    Arai, H
    Okada, S
    Sakurai, Y
    Yamaki, J
    [J]. SOLID STATE IONICS, 1997, 95 (3-4) : 275 - 282
  • [2] STRUCTURE AND ELECTROCHEMISTRY OF LI1+/-YNIO2 AND A NEW LI2NIO2 PHASE WITH THE NI(OH)2 STRUCTURE
    DAHN, JR
    VONSACKEN, U
    MICHAL, CA
    [J]. SOLID STATE IONICS, 1990, 44 (1-2) : 87 - 97
  • [3] RECHARGEABLE LINIO2 CARBON CELLS
    DAHN, JR
    VONSACKEN, U
    JUZKOW, MW
    ALJANABY, H
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1991, 138 (08) : 2207 - 2211
  • [4] STRUCTURE OF 1T-LI2NIO2 FROM POWDER NEUTRON-DIFFRACTION
    DAVIDSON, I
    GREEDAN, JE
    VONSACKEN, U
    MICHAL, CA
    DAHN, JR
    [J]. SOLID STATE IONICS, 1991, 46 (3-4) : 243 - 247
  • [5] STRUCTURAL CLASSIFICATION AND PROPERTIES OF THE LAYERED OXIDES
    DELMAS, C
    FOUASSIER, C
    HAGENMULLER, P
    [J]. PHYSICA B & C, 1980, 99 (1-4): : 81 - 85
  • [6] On the behavior of the LixNiO2 system:: an electrochemical and structural overview
    Delmas, C
    Peres, JP
    Rougier, A
    Demourgues, A
    Weill, F
    Chadwick, A
    Broussely, M
    Perton, F
    Biensan, P
    Willmann, P
    [J]. JOURNAL OF POWER SOURCES, 1997, 68 (01) : 120 - 125
  • [7] ALKALI METAL NICKEL OXIDES OF THE TYPE MNIO2
    DYER, LD
    BORIE, BS
    SMITH, GP
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1954, 76 (06) : 1499 - 1503
  • [8] Gozdz A. S., 1995, US Patent, Patent No. [5,418,091, 5418091]
  • [9] Cathode materials for lithium rocking chair batteries
    Koksbang, R
    Barker, J
    Shi, H
    Saidi, MY
    [J]. SOLID STATE IONICS, 1996, 84 (1-2) : 1 - 21
  • [10] IN-SITU X-RAY-DIFFRACTION AND ELECTROCHEMICAL STUDIES OF LI-1-XNIO2
    LI, W
    REIMERS, JN
    DAHN, JR
    [J]. SOLID STATE IONICS, 1993, 67 (1-2) : 123 - 130