P-Redox Mechanism at the Origin of the High Lithium Storage in NiP2-Based Batteries

被引：73

作者：

Boyanov, S. ^{[1
]}

Bernardi, J. ^{[1
]}

Bekaert, E. ^{[2
]}

Menetrier, M. ^{[2
]}

Doublet, M. -L. ^{[1
]}

Monconduit, L. ^{[1
]}

机构：

[1] Univ Montpellier 2, CNRS, Inst Charles Gerhardt, UMII UMI ENSCM, F-34095 Montpellier, France

[2] Univ Bordeaux, CNRS, ICMCB, F-33608 Pessac, France

来源：

CHEMISTRY OF MATERIALS | 2009年 / 21卷 / 02期

关键词：

LI-ION BATTERIES; NEGATIVE ELECTRODES; DIPHOSPHIDES; REACTIVITY; SPECTRA; METALS;

D O I：

10.1021/cm802393z

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：

The Li reactivity of NiP2 is investigated by means of electrochemical tests, in situ XRD, and T-31 NMR characterizations as well as first principles DFT calculations. A two-step insertion/conversion reaction is shown to transform the NiP2 starting electrode into an intermediate Li2NiP2 single phase and then to convert into the Li3P/Ni degrees nanocomposite. The ternary phase is fully characterized and is shown to be structurally very close to the starting NiP2 regarding the Ni ions environment. This demonstrates that its formation results from a P-redox insertion mechanism associated with a very good reversibility. However, its nucleation upon delithiation from the fully converted Li3P/Ni composite is shown to be kinetically limited (poor structural relationship) which strongly suggests that restricted lithiation is required for best cycleability of the NiP2/Li cell.

引用

页码：298 / 308

页数：11

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