Reaction energy for LiMn2O4 spinel dissolution in acid

被引：80

作者：

Benedek, R ^{[1
]}

Thackeray, MM ^{[1
]}

机构：

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

来源：

ELECTROCHEMICAL AND SOLID STATE LETTERS | 2006年 / 9卷 / 06期

关键词：

D O I：

10.1149/1.2188071

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

The dissolution of LiMn2O4 spinel in acid is a serious impediment to its use as a cathode material in Li batteries. In this paper, the free energy difference between reactants and products that drives the dissolution reaction is calculated using first principles methods for solid phases, and literature values for the solvation free energies of H, Li, and Mn ions and water molecules. We find that the dissolution reaction is endothermic in the absence of acid and exothermic in acid. Doping with Li on the Mn sublattice lowers the magnitude of the reaction energy Delta G by an amount proportional to the dilution of trivalent Mn in the host, thus confirming the role of disproportionation in the dissolution reaction.

引用

页码：A265 / A267

页数：3

共 36 条

[21] Computation of multi-component E-pH predominance diagrams [J].

Liu, HX ;

Zhang, CF .

CALPHAD-COMPUTER COUPLING OF PHASE DIAGRAMS AND THERMOCHEMISTRY, 2001, 25 (03) :363-380

[22] THERMODYNAMICS OF SOLVATION OF IONS .5. GIBBS FREE-ENERGY OF HYDRATION AT 298.15-K [J].

MARCUS, Y .

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1991, 87 (18) :2995-2999

[23] Chemical and magnetic characterization of spinel materials in the LiMn2O4-Li2Mn4O9-Li4Mn5O12 system [J].

Masquelier, C ;

Tabuchi, M ;

Ado, K ;

Kanno, R ;

Kobayashi, Y ;

Maki, Y ;

Nakamura, O ;

Goodenough, JB .

JOURNAL OF SOLID STATE CHEMISTRY, 1996, 123 (02) :255-266

[24] XPS study of reductive dissolution of 7Å-birnessite by H3AsO3, with constraints on reaction mechanism [J].

Nesbitt, HW ;

Canning, GW ;

Bancroft, GM .

GEOCHIMICA ET COSMOCHIMICA ACTA, 1998, 62 (12) :2097-2110

[25] Improvement of the cycleability of nano-crystalline lithium manganate cathodes by cation co-doping [J].

Nieto, S ;

Majumder, SB ;

Katiyar, RS .

JOURNAL OF POWER SOURCES, 2004, 136 (01) :88-98

[26] ATOMS, MOLECULES, SOLIDS, AND SURFACES - APPLICATIONS OF THE GENERALIZED GRADIENT APPROXIMATION FOR EXCHANGE AND CORRELATION [J].

PERDEW, JP ;

CHEVARY, JA ;

VOSKO, SH ;

JACKSON, KA ;

PEDERSON, MR ;

SINGH, DJ ;

FIOLHAIS, C .

PHYSICAL REVIEW B, 1992, 46 (11) :6671-6687

[27] Dopant-induced stabilization of rhombohedral LiMnO2 against Jahn-Teller distortion -: art. no. 134111 [J].

Prasad, R ;

Benedek, R ;

Thackeray, MM .

PHYSICAL REVIEW B, 2005, 71 (13)

[28] Electronic crystallization in a lithium battery material:: Columnar ordering of electrons and holes in the spinel LiMn2O4 [J].

Rodriguez-Carvajal, J ;

Rousse, G ;

Masquelier, C ;

Hervieu, M .

PHYSICAL REVIEW LETTERS, 1998, 81 (21) :4660-4663

[29] Microstrain and capacity fade in spinel manganese oxides [J].

Shin, YJ ;

Manthiram, A .

ELECTROCHEMICAL AND SOLID STATE LETTERS, 2002, 5 (03) :A55-A58

[30] A quantum chemical approach to the free energy calculations in condensed systems: The QM/MM method combined with the theory of energy representation [J].

Takahashi, H ;

Matubayasi, N ;

Nakahara, M ;

Nitta, T .

JOURNAL OF CHEMICAL PHYSICS, 2004, 121 (09) :3989-3999

← 1 2 3 4 →