What Happens to LiMnPO4 upon Chemical Delithiation?

被引:20
作者
Huang, Yiqing [1 ]
Chernova, Natasha A. [1 ]
Yin, Qiyue [2 ,3 ]
Wang, Qi [1 ]
Quackenbush, Nicholas F. [4 ]
Leskes, Michal [6 ]
Fang, Jin [1 ]
Omenya, Fredrick [1 ]
Zhang, Ruibo [1 ]
Wahila, Matthew J. [4 ]
Piper, Louis F. J. [4 ]
Zhou, Guangwen [2 ,3 ]
Grey, Clare P. [6 ]
Whittingham, M. Stanley [1 ,5 ]
机构
[1] SUNY Binghamton, Chem & Mat, Binghamton, NY 13902 USA
[2] SUNY Binghamton, Dept Mech Engn, Binghamton, NY 13902 USA
[3] SUNY Binghamton, Mat Sci & Engn Program, Binghamton, NY 13902 USA
[4] SUNY Binghamton, Dept Phys Appl Phys & Astron, Binghamton, NY 13902 USA
[5] SUNY Binghamton, NorthEast Ctr Chem Energy Storage NECCES, Binghamton, NY 13902 USA
[6] Univ Cambridge, Dept Chem, Lensfield Rd, Cambridge CB2 1EW, England
关键词
LITHIUM BATTERIES; CATHODE MATERIALS; ELECTRON-MICROSCOPY; PHASE-STABILITY; LIFEPO4; SPECTROSCOPY; TRANSITION; LIXMNPO4; OLIVINES; LICOPO4;
D O I
10.1021/acs.inorgchem.6b00089
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Olivine MnPO4 is the delithiated phase of the lithium-ion-battery cathode (positive electrode) material LiMnPO4, which is formed at the end of charge. This phase is metastable under ambient conditions and can only be produced by delithiation of LiMnPO4. We have revealed the manganese dissolution phenomenon during chemical delithiation of LiMnPO4, which causes amorphization of olivine MnPO4. The properties of crystalline MnPO4 obtained from carbon-coated LiMnPO4 and of the amorphous product resulting from delithiation of pure LiMnPO4 were studied and compared. The phosphorus-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P2O7 from NMR, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analysis. The thermal stability of MnPO4 is significantly higher under high vacuum than at ambient condition, which is shown to be related to surface water removal.
引用
收藏
页码:4335 / 4343
页数:9
相关论文
共 30 条
[1]  
[Anonymous], 1987, GEN STRUCTURE ANAL S
[2]   Phase transitions occurring upon lithium insertion-extraction of LiCoPO4 [J].
Bramnik, Natalia N. ;
Nikolowski, Kristian ;
Baehtz, Carsten ;
Bramnik, Kirill G. ;
Ehrenberg, Helmut .
CHEMISTRY OF MATERIALS, 2007, 19 (04) :908-915
[3]   Thermal instability of Olivine-type LiMnPO4 cathodes [J].
Chen, Guoying ;
Richardson, Thomas J. .
JOURNAL OF POWER SOURCES, 2010, 195 (04) :1221-1224
[4]   Electron microscopy study of the LiFePO4 to FePO4 phase transition [J].
Chen, GY ;
Song, XY ;
Richardson, TJ .
ELECTROCHEMICAL AND SOLID STATE LETTERS, 2006, 9 (06) :A295-A298
[5]   The hydrothermal synthesis and characterization of olivines and related compounds for electrochemical applications [J].
Chen, Jiajun ;
Vacchio, Michael J. ;
Wang, Shijun ;
Chernova, Natalya ;
Zavalij, Peter Y. ;
Whittingham, M. Stanley .
SOLID STATE IONICS, 2008, 178 (31-32) :1676-1693
[6]   Toward understanding of electrical limitations (electronic, ionic) in LiMPO4 (M = Fe, Mn) electrode materials [J].
Delacourt, C ;
Laffont, L ;
Bouchet, R ;
Wurm, C ;
Leriche, JB ;
Morcrette, M ;
Tarascon, JM ;
Masquelier, C .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2005, 152 (05) :A913-A921
[7]   One-step low-temperature route for the preparation of electrochemically active LiMnPO4 powders [J].
Delacourt, C ;
Poizot, P ;
Morcrette, M ;
Tarascon, JM ;
Masquelier, C .
CHEMISTRY OF MATERIALS, 2004, 16 (01) :93-99
[8]  
Durif A., 1996, TOPICS PHOSPHATE CHE
[9]   Understanding the stability of MnPO4 [J].
Huang, Yiqing ;
Fang, Jin ;
Omenya, Fredrick ;
O'Shea, Martin ;
Chernova, Natasha A. ;
Zhang, Ruibo ;
Wang, Qi ;
Quackenbush, Nicholas F. ;
Piper, Louis F. J. ;
Scanlon, David O. ;
Whittingham, M. Stanley .
JOURNAL OF MATERIALS CHEMISTRY A, 2014, 2 (32) :12827-12834
[10]   Isotropic High Field NMR Spectra of Li-Ion Battery Materials with Anisotropy >1 MHz [J].
Hung, Ivan ;
Zhou, Lina ;
Pourpoint, Frederique ;
Grey, Clare P. ;
Gan, Zhehong .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (04) :1898-1901