Degradation and (de)lithiation processes in the high capacity battery material LiFeBO

被引:54
作者
Bo, Shou-Hang [1 ]
Wang, Feng [2 ]
Janssen, Yuri [1 ]
Zeng, Dongli [1 ,2 ]
Kyung-Wan Nam [2 ]
Xu, Wenqian [3 ]
Du, Lin-Shu [1 ]
Graetz, Jason [2 ]
Yang, Xiao-Qing [2 ]
Zhu, Yimei [2 ]
Parise, John B. [3 ]
Grey, Clare P. [1 ,4 ]
Khalifah, Peter G. [1 ,2 ]
机构
[1] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11794 USA
[2] Brookhaven Natl Lab, Upton, NY 11973 USA
[3] SUNY Stony Brook, Dept Geosci, Stony Brook, NY 11794 USA
[4] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England
关键词
D O I
10.1039/c2jm16436a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Lithium iron borate (LiFeBO3)is a particularly desirable cathode material for lithium-ion batteries due to its high theoretical capacity (220 mA h g(-1)) and its favorable chemical constituents, which are abundant, inexpensive and non-toxic. However, its electrochemical performance appears to be severely hindered by the degradation that results from air or moisture exposure. The degradation of LiFeBO3 was studied through a wide array of ex situ and in situ techniques (X-ray diffraction, nuclear magnetic resonance, X-ray absorption spectroscopy, electron microscopy and spectroscopy) to better understand the possible degradation process and to develop methods for preventing degradation. It is demonstrated that degradation involves both Li loss from the framework of LiFeBO3 and partial oxidation of Fe(II), resulting in the creation of a stable lithium-deficient phase with a similar crystal structure to LiFeBO3. Considerable LiFeBO3 degradation occurs during electrode fabrication, which greatly reduces the accessible capacity of LiFeBO3 under all but the most stringently controlled conditions for electrode fabrication. Comparative studies on micron-sized LiFeBO3 and nanoscale LiFeBO3-carbon composite showed a very limited penetration depth (similar to 30 nm) of the degradation phase front into the LiFeBO3 core under near-ambient conditions. Two-phase reaction regions during delithiation and lithiation of LiFeBO3 were unambiguously identified through the galvanostatic intermittent titration technique (GITT), although it is still an open question as to whether the two-phase reaction persists across the whole range of possible Li contents. In addition to the main intercalation process with a thermodynamic potential of 2.8 V, there appears to be a second reversible electrochemical process with a potential of 1.8 V. The best electrochemical performance of LiFeBO3 was ultimately achieved by introducing carbon to minimize the crystallite size and strictly limiting air and moisture exposure to inhibit degradation.
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页码:8799 / 8809
页数:11
相关论文
共 13 条
  • [1] Building better batteries
    Armand, M.
    Tarascon, J. -M.
    [J]. NATURE, 2008, 451 (7179) : 652 - 657
  • [2] MAS NMR Study of the Metastable Solid Solutions Found in the LiFePO4/FePO4 System
    Cabana, Jordi
    Shirakawa, Junichi
    Chen, Guoying
    Richardson, Thomas J.
    Grey, Clare P.
    [J]. CHEMISTRY OF MATERIALS, 2010, 22 (03) : 1249 - 1262
  • [3] The structure and electrochemical performance of LiFeBO3 as a novel Li-battery cathode material
    Dong, Y. Z.
    Zhao, Y. M.
    Shi, Z. D.
    An, X. N.
    Fu, P.
    Chen, L.
    [J]. ELECTROCHIMICA ACTA, 2008, 53 (05) : 2339 - 2345
  • [4] NMR studies of cathode materials for lithium-ion rechargeable batteries
    Grey, CP
    Dupré, N
    [J]. CHEMICAL REVIEWS, 2004, 104 (10) : 4493 - 4512
  • [5] The effects of moderate thermal treatments under air on LiFePO4-based nano powders
    Hamelet, Stephane
    Gibot, Pierre
    Casas-Cabanas, Montse
    Bonnin, Dominique
    Grey, Clare P.
    Cabana, Jordi
    Leriche, Jean-Bernard
    Rodriguez-Carvajal, Juan
    Courty, Matthieu
    Levasseur, Stephane
    Carlach, Philippe
    van Thournout, Michele
    Tarascon, Jean-Marie
    Masquelier, Christian
    [J]. JOURNAL OF MATERIALS CHEMISTRY, 2009, 19 (23) : 3979 - 3991
  • [6] JANSSEN Y, UNPUB
  • [7] Linking Local Environments and Hyperfine Shifts: A Combined Experimental and Theoretical 31P and 7Li Solid-State NMR Study of Paramagnetic Fe(III) Phosphates
    Kim, Jongsik
    Middlemiss, Derek S.
    Chernova, Natasha A.
    Zhu, Ben Y. X.
    Masquelier, Christian
    Grey, Clare P.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (47) : 16825 - 16840
  • [8] LiMBO3 (M = Mn, Fe, Co):: synthesis, crystal structure and lithium deinsertion/insertion properties
    Legagneur, V
    An, Y
    Mosbah, A
    Portal, R
    La Salle, AL
    Verbaere, A
    Guyomard, D
    Piffard, Y
    [J]. SOLID STATE IONICS, 2001, 139 (1-2) : 37 - 46
  • [9] ATHENA, ARTEMIS, HEPHAESTUS:: data analysis for X-ray absorption spectroscopy using IFEFFIT
    Ravel, B
    Newville, M
    [J]. JOURNAL OF SYNCHROTRON RADIATION, 2005, 12 : 537 - 541
  • [10] First-principles study on lithium metal borate cathodes for lithium rechargeable batteries
    Seo, Dong-Hwa
    Park, Young-Uk
    Kim, Sung-Wook
    Park, Inchul
    Shakoor, R. A.
    Kang, Kisuk
    [J]. PHYSICAL REVIEW B, 2011, 83 (20):