Crystal structure and lithium insertion properties of orthorhombic Li2TiFe(PO4)3 and Li2TiCr(PO4)3

被引：25

作者：

Patoux, S

Rousse, G

Leriche, JB

Masquelier, C

机构：

[1] Univ Picardie, CNRS, Lab React & Chim Solides, UMR 6007, F-80039 Amiens, France

[2] Univ Paris 06, Lab Phys Milieux Condenses, F-75252 Paris 05, France

来源：

SOLID STATE SCIENCES | 2004年 / 6卷 / 10期

关键词：

lithium; phosphates; anti-NASICON; positive electrodes; lithium batteries;

D O I：

10.1016/j.solidstatesciences.2004.07.028

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The crystal structures of orthorhombic Li2TiFe(PO4)(3) and Li2TiCr(PO4)(3) were determined from Rietveld refinement of neutron powder diffraction data. Both compounds are isostructural in the Pbna space group with a = 8.543(1) Angstrom, b = 8.623(1) Angstrom, c = 11.978(1) Angstrom and a = 8.505(1) Angstrom, b = 8.589(1) Angstrom, c = 11.929(1) Angstrom, respectively. Lithium ions are located in a single four-fold coordinated site Li(1). Electrochemical insertion of lithium proceeds through the reduction of Fe3+ into Fe2+ (similar to 2.8 V vs. Li+/Li) and Ti4+ into Ti3+ (similar to 2.5 V vs. Li+/Li) towards the new compositions Li3TiCr(PO4)(3) and Li4TiFe(PO4)(3). In situ X-ray diffraction and potentiostatic intermittent titration technique indicate a solid solution mechanism for the reversible lithium insertion/extraction. Chemical reaction of Li2TiFe(PO4)3 with n-BuLi leads to orthorhombic Li4TiFe(PO4)3. (C) 2004 Elsevier SAS. All rights reserved.

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页码：1113 / 1120

页数：8

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