Thermodynamics of Lithium in TiO2(B) from First Principles

被引：86

作者：

Dalton, Andrew S. ^{[1
]}

Belak, Anna A. ^{[1
]}

Van der Ven, Anton ^{[1
]}

机构：

[1] Univ Michigan, Dept Mat Sci & Engn, Ann Arbor, MI 48109 USA

来源：

CHEMISTRY OF MATERIALS | 2012年 / 24卷 / 09期

关键词：

lithium; intercalation; titanium dioxide; TiO2(B); cluster expansion; Monte Carlo; INITIO MOLECULAR-DYNAMICS; TOTAL-ENERGY CALCULATIONS; PHASE-STABILITY; INSERTION; NANOWIRES; SURFACE; COMPUTATION; NANOTUBES; LIXTIO2; ANATASE;

D O I：

10.1021/cm203283v

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：

We use first-principles density functional theory (DFT) calculations combined with statistical mechanical techniques based on the cluster expansion method and Monte Carlo simulations to predict the lithium site occupancies, voltage curves, and phase diagram for TiO2(B), a candidate anode material for lithium ion batteries. We find that Li intercalation is thermodynamically favorable up to a Li/Ti ratio of 1.25, higher than the theoretical maximum usually assumed for TiO2. The calculated phase diagram at 300 K contains three first-order phase transformations corresponding to major changes in the favored intercalation sites at increasing Li concentrations. Calculations based on DFT predict the stability of a new Li site at high Li concentrations in TiO2(B) and the occurrence of a dramatic site-inversion as Li is added to the host.

引用

页码：1568 / 1574

页数：7