A New Insight into the Polaron-Li Complex Diffusion in Cathode Material LiFe1-yMnyPO4 for Li Ion Batteries

被引：20

作者：

Dinh, Van An ^{[1
]}

Nara, Jun ^{[2
]}

Ohno, Takahisa ^{[1
,2
]}

机构：

[1] Global Res Ctr Nanomat Sci Energy & Environm GREE, Tsukuba, Ibaraki 3050047, Japan

[2] Natl Inst Mat Sci, CMSU, Tsukuba, Ibaraki 3050047, Japan

来源：

APPLIED PHYSICS EXPRESS | 2012年 / 5卷 / 04期

关键词：

PHOSPHO-OLIVINES; LITHIUM; LIMNPO4; MN; FE;

D O I：

10.1143/APEX.5.045801

中图分类号：

O59 [应用物理学];

学科分类号：

摘要：

Based on the Heyd-Scuseria-Ernzerhof hybrid density functionals study, we proposed a new insight into the diffusion of polaron-Li vacancy complexes in LiFe1-yMnyPO4 (y = 0, 1/2, 1). It is found that the polaron migrates along a crossing or a parallel path relative to the Li moving direction. In LiFePO4, the complex diffusion along the zigzag pathway is favorable and has a barrier of 600 meV, while the diffusion along the parallel pathway with a barrier of 623 meV is favorable in LiMnPO4. For LiFe1/2Mn1/2PO4, since the polaron is formed within a single Fe layer, the diffusion proceeds along the parallel pathway with a barrier of 635 meV. (C) 2012 The Japan Society of Applied Physics

引用

页数：3

共 23 条

[1] Formation and diffusion of vacancy-polaron complex in olivine-type LiMnPO4 and LiFePO4 [J].

Asari, Yusuke ;

Suwa, Yuji ;

Hamada, Tomoyuki .

PHYSICAL REVIEW B, 2011, 84 (13)

[2] Electronically conductive phospho-olivines as lithium storage electrodes [J].

Chung, SY ;

Bloking, JT ;

Chiang, YM .

NATURE MATERIALS, 2002, 1 (02) :123-128

[3] Toward understanding of electrical limitations (electronic, ionic) in LiMPO4 (M = Fe, Mn) electrode materials [J].

Delacourt, C ;

Laffont, L ;

Bouchet, R ;

Wurm, C ;

Leriche, JB ;

Morcrette, M ;

Tarascon, JM ;

Masquelier, C .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2005, 152 (05) :A913-A921

[4] Small polaron hopping in LixFePO4 solid solutions:: Coupled lithium-ion and electron mobility [J].

Ellis, Brian ;

Perry, Laura K. ;

Ryan, Dominic H. ;

Nazar, L. F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (35) :11416-11422

[5] Influence of the structure on the electrochemical performance of lithium transition metal phosphates as cathodic materials in rechargeable lithium batteries:: A new high-pressure form of LiMPO4 (M = Fe and Ni) [J].

García-Moreno, O ;

Alvarez-Vega, M ;

García-Alvarado, F ;

García-Jaca, J ;

Gallardo-Amores, JM ;

Sanjuán, ML ;

Amador, U .

CHEMISTRY OF MATERIALS, 2001, 13 (05) :1570-1576

[6] Anti-Site Defects and Ion Migration in the LiFe0.5Mn0.5PO4 Mixed-Metal Cathode Material [J].

Gardiner, Grahame R. ;

Islam, M. Saiful .

CHEMISTRY OF MATERIALS, 2010, 22 (03) :1242-1248

[7] A climbing image nudged elastic band method for finding saddle points and minimum energy paths [J].

Henkelman, G ;

Uberuaga, BP ;

Jónsson, H .

JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (22) :9901-9904

[8]

Heyd J, 2006, J CHEM PHYS, V124, DOI [10.1063/1.2204597, 10.1063/1.1564060]

[9] Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set [J].

Kresse, G ;

Furthmuller, J .

PHYSICAL REVIEW B, 1996, 54 (16) :11169-11186

[10] LiMnPO4 as the cathode for lithium batteries [J].

Li, GH ;

Azuma, H ;

Tohda, M .

ELECTROCHEMICAL AND SOLID STATE LETTERS, 2002, 5 (06) :A135-A137

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