Thermodynamic and kinetic studies of electrochemical lithium insertion into quaternary Li-Mn-V-O spinel as positive materials for rechargeable lithium batteries

Journal Article · Mon Nov 01 04:00:00 EST 1993 · Journal of the Electrochemical Society; (United States)

DOI:https://doi.org/10.1149/1.2221009· OSTI ID:5696196

Kumagai, Naoaki; Fujiwara, Takayuki; Tanno, Kazuo ^[1]; Horiba, Tatsuo ^[2]

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1. Iwate Univ., Morioka (Japan). Dept. of Applied Chemistry and Molecular Science
2. Hitachi Ltd. (Japan). Hitachi Research Lab.

The thermodynamics and kinetics of the lithium insertion process into the quaternary spinel Li[sub x]Mn[sub 2]O[sub 4] [times] yV[sub 2]O[sub 5](x = 0.5 to 3, y = 0.25 to 0.5) have been studied. The partial molar quantities [Delta][bar G][sub Li(x)], [Delta][bar H][sub Li(x)], and [Delta][bar S][sub Si(x)] of lithium in the quaternary spinels have been determined from electromotive force-temperature measurements performed using 1M LiClO[sub 4] solution of propylene carbonate in the temperature range from 298 to 330 K. These thermodynamic functions varied with the lithium concentration in the oxide structure and a major variation was observed around x = 1 in Li[sub x]Mn[sub 2]O[sub 4] [times] yV[sub 2]O[sub 5]. The chemical diffusion coefficient for lithium [tilde D] in the spinel oxides has been measured as functions of the lithium composition and temperature by a current-pulse relaxation technique. The values of [tilde D], obtained in the x value range from 0.5 to 1.0 at 298K, were found to be several orders of magnitude higher than those in the x value range from 1.3 to 2.5. The lithium self-diffusion coefficient D[sub Li], partial lithium-ion conductivity and activation energy for lithium diffusion have been calculated.

• OSTI ID: 5696196
• Journal Information: Journal of the Electrochemical Society; (United States), Journal Name: Journal of the Electrochemical Society; (United States) Vol. 140:11; ISSN JESOAN; ISSN 0013-4651
• Country of Publication: United States
• Language: English

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