Electrochemical Delithiation/Relithiation of LiCoPO4: A Two-Step Reaction Mechanism Investigated by in Situ X-ray Diffraction, in Situ X-ray Absorption Spectroscopy, and ex Situ 7Li/31P NMR Spectroscopy

被引：51

作者：

Kaus, Maximilian ^{[1
]}

Issac, Ibrahim ^{[1
]}

Heinzmann, Ralf ^{[1
,2
]}

Doyle, Stephen ^{[3
]}

Mangold, Stefan ^{[3
]}

Hahn, Horst ^{[1
,4
]}

Chakravadhanula, Venkata Sai Kiran ^{[4
]}

Kuebel, Christian ^{[1
,4
]}

Ehrenberg, Helmut ^{[4
,5
]}

Indris, Sylvio ^{[1
,4
,5
]}

机构：

[1] Karlsruhe Inst Technol, Inst Nanotechnol, D-76021 Karlsruhe, Germany

[2] Bruker Biospin GmbH, D-76287 Rheinstetten, Germany

[3] Karlsruhe Inst Technol, ANKA Synchrotron Radiat Facil, D-76021 Karlsruhe, Germany

[4] Helmholtz Inst Ulm Electrochem Energy Storage, D-76021 Karlsruhe, Germany

[5] Karlsruhe Inst Technol, Inst Appl Mat Energy Storage Syst, D-76021 Karlsruhe, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2014年 / 118卷 / 31期

关键词：

IMPROVED CYCLING PERFORMANCE; CATHODE MATERIALS; DISCHARGE CAPACITY; LITHIUM; CARBON; FE; CONDUCTIVITY; LIPF6; 1ST-PRINCIPLES; ELECTROLYTES;

D O I：

10.1021/jp503306v

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：

LiCoPO4 was synthesized by a solid-state and a supercritical solvo-thermal method. In situ X-ray absorption near-edge structure (XANES) experiments were evaluated on the basis of full-cycle experiments confirming the predominantly reversible character of the redox reaction. In situ X-ray diffraction (XRD) measurements were performed to follow structural changes during cycling indicating the existence of an intermediate phase upon cycling. The local phosphorus and lithium environments were studied by ex situ P-31 and Li-7 NMR at different states of charge proving the existence of an intermediate phase of the composition Li2/3CoPO4. On the basis of these findings, a model of the (de)lithiation process of LiCoPO4 is developed and discussed.

引用

页码：17279 / 17290

页数：12

共 54 条

[1] Functional electrolytes: Novel type additives for cathode materials, providing high cycleability performance [J].

Abe, K ;

Ushigoe, Y ;

Yoshitake, H ;

Yoshio, M .

JOURNAL OF POWER SOURCES, 2006, 153 (02) :328-335

[2] High-Voltage Electrolytes Based on Adiponitrile for Li-Ion Batteries [J].

Abu-Lebdeh, Yaser ;

Davidson, Isobel .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2009, 156 (01) :A60-A65

[3] Improved cycle life of Fe-substituted LiCoPO4 [J].

Allen, J. L. ;

Jow, T. R. ;

Wolfenstine, J. .

JOURNAL OF POWER SOURCES, 2011, 196 (20) :8656-8661

[4] Olivine LiCoPO4 as 4.8 V electrode material for lithium batteries [J].

Amine, K ;

Yasuda, H ;

Yamachi, M .

ELECTROCHEMICAL AND SOLID STATE LETTERS, 2000, 3 (04) :178-179

[5]

Bacq O. L., 2004, PHYS REV B, V69

[6] Thermal stability of LiCoPO4 cathodes [J].

Bramnik, Natalia N. ;

Nikolowski, Kristian ;

Trots, Dmytro M. ;

Ehrenberg, Helmut .

ELECTROCHEMICAL AND SOLID STATE LETTERS, 2008, 11 (06) :A89-A93

[7] 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

[8] Electrochemical and structural study of LiCoPO4-based electrodes [J].

Bramnik, NN ;

Bramnik, KG ;

Buhrmester, T ;

Baehtz, C ;

Ehrenberg, H ;

Fuess, H .

JOURNAL OF SOLID STATE ELECTROCHEMISTRY, 2004, 8 (08) :558-564

[9] Confirmation of the Domino-Cascade Model by LiFePO4/FePO4 Precession Electron Diffraction [J].

Brunetti, G. ;

Robert, D. ;

Bayle-Guillemaud, P. ;

Rouviere, J. L. ;

Rauch, E. F. ;

Martin, J. F. ;

Colin, J. F. ;

Bertin, F. ;

Cayron, C. .

CHEMISTRY OF MATERIALS, 2011, 23 (20) :4515-4524

[10] Effect of organic additives on the cycling performances of lithium metal polymer cells [J].

Choi, Ji-Ae ;

Eo, Seung-Min ;

MacFarlane, Douglas R. ;

Forsyth, Maria ;

Cha, Eunhee ;

Kim, Dong-Won .

JOURNAL OF POWER SOURCES, 2008, 178 (02) :832-836

← 1 2 3 4 5 6 →