First-principles study on lithium removal from Li2MnO3

被引：173

作者：

Koyama, Yukinori ^{[1
]}

Tanaka, Isao ^{[1
]}

Nagao, Miki ^{[2
]}

Kanno, Ryoji ^{[2
]}

机构：

[1] Kyoto Univ, Dept Mat Sci & Engn, Sakyo Ku, Kyoto 6068501, Japan

[2] Tokyo Inst Technol, Dept Elect Chem, Midori Ku, Yokohama, Kanagawa 2268502, Japan

来源：

JOURNAL OF POWER SOURCES | 2009年 / 189卷 / 01期

关键词：

First-principles calculation; Lithium manganese oxide; Crystallographic structure; Redox potential; Charge compensation; X-RAY-DIFFRACTION; AB-INITIO; SOLID-SOLUTIONS; 1ST PRINCIPLES; CATION; MECHANISM; SYSTEM;

D O I：

10.1016/j.jpowsour.2008.07.073

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：

A systematic first-principles calculation based on density functional theory is carried out to discuss the redox mechanism of Li2MnO3. The lattices of structural models having C2/m- and C2/c-type stacking sequences can be regarded as hexagonal, while their symmetry is monoclinic. Different stacking sequences of [Mn2/3Li1/3] layers do not cause differences in the energy or crystallographic structure, suggesting a disordered stacking sequence. A calculation for Li2-xMnO3 assuming topotactic lithium removal indicates that lithium removal can occur at a potential of about 4.6 V with a wide potential plateau. The electronic structure of Li2-xMnO3 shows that the manganese ions remain in the charge state of Mn4+ and the charge of the removed lithium ions is compensated by the oxidation of oxygen. (C) 2008 Elsevier B.V. All rights reserved.

引用

页码：798 / 801

页数：4

共 26 条

[1] Local structure and first cycle redox mechanism of layered Li1.2Cr0.4Mn0.4O2 cathode material [J].

Ammundsen, B ;

Paulsen, J ;

Davidson, I ;

Liu, RS ;

Shen, CH ;

Chen, JM ;

Jang, LY ;

Lee, JF .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2002, 149 (04) :A431-A436

[2] Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides [J].

Aydinol, MK ;

Kohan, AF ;

Ceder, G ;

Cho, K ;

Joannopoulos, J .

PHYSICAL REVIEW B, 1997, 56 (03) :1354-1365

[3] IMPROVED TETRAHEDRON METHOD FOR BRILLOUIN-ZONE INTEGRATIONS [J].

BLOCHL, PE ;

JEPSEN, O ;

ANDERSEN, OK .

PHYSICAL REVIEW B, 1994, 49 (23) :16223-16233

[4] High-resolution X-ray diffraction, DIFFaX, NMR and first principles study of disorder in the Li2MnO3-Li[Ni1/2Mn1/2]O2 solid solution [J].

Bréger, J ;

Jiang, M ;

Dupré, N ;

Meng, YS ;

Shao-Horn, Y ;

Ceder, G ;

Grey, CP .

JOURNAL OF SOLID STATE CHEMISTRY, 2005, 178 (09) :2575-2585

[5] Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study [J].

Dudarev, SL ;

Botton, GA ;

Savrasov, SY ;

Humphreys, CJ ;

Sutton, AP .

PHYSICAL REVIEW B, 1998, 57 (03) :1505-1509

[6] The significance of the Li2MnO3 component in 'composite' xLi2MnO3 • (1-x)LiMn0.5Ni0.5O2 electrodes [J].

Johnson, CS ;

Kim, JS ;

Lefief, C ;

Li, N ;

Vaughey, JT ;

Thackeray, MM .

ELECTROCHEMISTRY COMMUNICATIONS, 2004, 6 (10) :1085-1091

[7] Electrochemical and structural properties of xLi2M'O3•(1-x)LiMn0.5Ni0.5O2 eIectrodes for lithium batteries (M' = Ti, Mn, Zr; 0 ≤ x ≤ 0.3) [J].

Kim, JS ;

Johnson, CS ;

Vaughey, JT ;

Thackeray, MM ;

Hackney, SA .

CHEMISTRY OF MATERIALS, 2004, 16 (10) :1996-2006

[8] First principles calculations of formation energies and electronic structures of defects in oxygen-deficient LiMn2O4 [J].

Koyama, Y ;

Tanaka, I ;

Adachi, H ;

Uchimoto, Y ;

Wakihara, M .

JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2003, 150 (01) :A63-A67

[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] STRUKTURVERGLEICHE AN TERNAREN UND QUARTERNAREN OXIDEN [J].

LANG, G .

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1966, 348 (5-6) :246-&

← 1 2 3 →