Free energy for protonation reaction in lithium-ion battery cathode materials

被引：60

作者：

Benedek, R. ^{[1
]}

Thackeray, M. M. ^{[1
]}

van de Walle, A. ^{[2
]}

机构：

[1] Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA

[2] CALTECH, Div Engn & Appl Sci, Pasadena, CA 91125 USA

来源：

CHEMISTRY OF MATERIALS | 2008年 / 20卷 / 17期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1021/cm703042r

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：

Calculations are performed of free energies for proton-for-lithium-ion exchange reactions in lithium-ion battery cathode materials. First-principles calculations are employed for the solid phases and tabulated ionization potential and hydration energy data for aqueous ions. Layered structures, spinel LiMn2 O-4, and olivine LiFePO4 are considered. Protonation is most favorable energetically in layered systems, such as Li-2 MnO3 and LiCoO2. Less favorable are ion-exchange in spinel LiMn2 O-4 and LiV3 O-8. Unfavorable is the Substitution of protons for Li in olivine LiFePO4, because of the large distortion of the Fe and P coordination polyhedra. The reaction free energy scales roughly linearly with the volume change in the reaction.

引用

页码：5485 / 5490

页数：6

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