Enthalpy of formation of Li1+xMn2-xO4 (0 < x < 0.1) spinel phases

被引:27
作者
Cupid, Damian M. [1 ]
Reif, Alexandra [1 ]
Seifert, Hans J. [1 ]
机构
[1] Karlsruhe Inst Technol, Inst Appl Mat IAM AWP, D-76344 Eggenstein Leopoldshafen, Germany
关键词
Li1+xMn2-xO4; Spinel; Oxide solution calorimetry; Enthalpy of formation; Lithium-ion battery; CATHODE ACTIVE MATERIAL; MN-O SPINEL; STABILITY; PERFORMANCE; DIAGRAM;
D O I
10.1016/j.tca.2014.11.003
中图分类号
O414.1 [热力学];
学科分类号
摘要
The enthalpies of formation of Li1-xMn2-xO4 (0 < x < 0.1) spinel phases were measured using high temperature oxide solution calorimetry in a sodium molybdate solvent at 701 C. One commercially available LiMn2O4 powder and two Li1-xMn2-xO4 samples synthesized using the sol-gel method were used for the measurements. The enthalpies of formation of the spinels from the binary constituent oxides and from the elements become more exothermic with increasing lithium content and increasing average oxidation state of the manganese cation in the range 0 < x < 0.1. Additionally, the lithium-rich boundary of the Li1-xMn2-xO4 phase for 0 < x < 0.1 was re-investigated using differential thermal analysis combined with thermogravimetric analysis. (C) 2014 Elsevier B.V. All rights reserved.
引用
收藏
页码:35 / 41
页数:7
相关论文
共 14 条
[1]   Investigation of the lithium-rich boundary of the Li1+xMn2-xO4 cubic spinel phase in air [J].
Cupid, Damian M. ;
Lehmann, Toni ;
Bergfeldt, Thomas ;
Berndt, Harald ;
Seifert, Hans J. .
JOURNAL OF MATERIALS SCIENCE, 2013, 48 (09) :3395-3403
[2]   The high temperature phase diagram of Li1+xMn2-xO4 and its implications [J].
Gao, Y ;
Dahn, JR .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1996, 143 (06) :1783-1788
[3]   Thermodynamic investigation and cathode performance of Li-Mn-O spinel system as cathode active material for lithium secondary battery [J].
Idemoto, Y ;
Ozasa, T ;
Koura, N .
JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, 2001, 109 (09) :771-776
[4]   Thermodynamic stability and cathode performance of Li1+xMn2-xO4 as a cathode active material for lithium secondary battery [J].
Idemoto, Y ;
Ogawa, S ;
Uemura, Y ;
Koura, N .
JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, 2000, 108 (09) :848-853
[5]   Stability and defect structure of spinels Li1+xMn2-xO4-δ :: I.: In situ investigations on the stability field of the spinel phase [J].
Luo, Chunhui ;
Martin, Manfred .
JOURNAL OF MATERIALS SCIENCE, 2007, 42 (06) :1955-1964
[6]   Progress and new directions in high temperature calorimetry revisited [J].
Navrotsky, A .
PHYSICS AND CHEMISTRY OF MINERALS, 1997, 24 (03) :222-241
[7]   PROGRESS AND NEW DIRECTIONS IN HIGH-TEMPERATURE CALORIMETRY [J].
NAVROTSKY, A .
PHYSICS AND CHEMISTRY OF MINERALS, 1977, 2 (1-2) :89-104
[8]   Phase diagram of Li-Mn-O spinel in air [J].
Paulsen, JM ;
Dahn, JR .
CHEMISTRY OF MATERIALS, 1999, 11 (11) :3065-3079
[9]  
Robie R. A., 1992, THERMODYNAMIC PROPER
[10]   The thermal stability of lithium-manganese-oxide spinel phases [J].
Thackeray, MM ;
Mansuetto, MF ;
Dees, DW ;
Vissers, DR .
MATERIALS RESEARCH BULLETIN, 1996, 31 (02) :133-140