Mechanisms of manganese spinels dissolution and capacity fade at high temperature
Tests on the stability of spinels stored at different states of charge were performed. It was found that Mn dissolution took place irreversibly from the charged state with formation of MnF 2, ramsdellite–Li 0.5MnO 2. In the discharged state, the Mn at the surface of the LiMn 2O 4 was in equilibrium...
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| Published in | Journal of power sources Vol. 97; pp. 377 - 380 |
|---|---|
| Main Authors | , , , |
| Format | Journal Article Conference Proceeding |
| Language | English |
| Published |
Lausanne
Elsevier B.V
01.07.2001
Elsevier Sequoia |
| Subjects | |
| Online Access | Get full text |
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| Abstract | Tests on the stability of spinels stored at different states of charge were performed. It was found that Mn dissolution took place irreversibly from the charged state with formation of MnF
2, ramsdellite–Li
0.5MnO
2. In the discharged state, the Mn at the surface of the LiMn
2O
4 was in equilibrium with a soluble species, which leads to an increase in the cathode resistance. It was found that the amount of the dissolved Mn increased with increasing LiPF
6 concentration and that 2
equiv. of PO
2F
2
− were generated. Concurrent formation of carbonate decomposition products, such as CO
2, C
2H
4, EtOH, Et
2O, and AcOEt, suggests that the mechanism of Mn dissolution from the charged state was composed of the following steps: the initial decarboxylation of electrolyte catalyzed by λMnO
2 to give EtOH, followed by reduction of λMnO
2 by EtOH to give acetate and MnO, and then Mn dissolution via MnO bond activation assisted by LiPF
6. |
|---|---|
| AbstractList | Tests on the stability of spinels stored at different states of charge were performed. It was found that Mn dissolution took place irreversibly from the charged state with formation of MnF
2, ramsdellite–Li
0.5MnO
2. In the discharged state, the Mn at the surface of the LiMn
2O
4 was in equilibrium with a soluble species, which leads to an increase in the cathode resistance. It was found that the amount of the dissolved Mn increased with increasing LiPF
6 concentration and that 2
equiv. of PO
2F
2
− were generated. Concurrent formation of carbonate decomposition products, such as CO
2, C
2H
4, EtOH, Et
2O, and AcOEt, suggests that the mechanism of Mn dissolution from the charged state was composed of the following steps: the initial decarboxylation of electrolyte catalyzed by λMnO
2 to give EtOH, followed by reduction of λMnO
2 by EtOH to give acetate and MnO, and then Mn dissolution via MnO bond activation assisted by LiPF
6. Tests on the stability of spinels stored at different states of charge were performed. It was found that Mn dissolution took place irreversibly from the charged state with formation of MnF sub(2), ramsdellite-Li sub(0.5)MnO sub(2). In the discharged state, the Mn at the surface of the LiMn sub(2)O sub(4) was in equilibrium with a soluble species, which leads to an increase in the cathode resistance. It was found that the amount of the dissolved Mn increased with increasing LiPF sub(6) concentration and that 2 equiv. of PO sub(2)F super(-) sub(2) were generated. Concurrent formation of carbonate decomposition products, such as CO sub(2), C sub(2)H sub(4), EtOH, Et sub(2)O, and AcOEt, suggests that the mechanism of Mn dissolution from the charged state was composed of the following steps: the initial decarboxylation of electrolyte catalyzed by lambda MnO sub(2) to give EtOH, followed by reduction of lambda MnO sub(2) by EtOH to give acetate and MnO, and then Mn dissolution via Mn-O bond activation assisted by LiPF sub(6). copyright 2001 Elsevier Science B.V. |
| Author | Kiyohara, Chikara Okahara, Kenji Aoshima, Takayuki Shizuka, Kenji |
| Author_xml | – sequence: 1 givenname: Takayuki surname: Aoshima fullname: Aoshima, Takayuki email: taoshima@rc.m-kagaku.co.jp – sequence: 2 givenname: Kenji surname: Okahara fullname: Okahara, Kenji – sequence: 3 givenname: Chikara surname: Kiyohara fullname: Kiyohara, Chikara – sequence: 4 givenname: Kenji surname: Shizuka fullname: Shizuka, Kenji |
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| Keywords | Lithium manganese oxides Storage Capacity fade Mn dissolution Ternary compound Performance evaluation Alkali metal Compounds Transition metal Compounds Secondary cell Electrode material Electric batteries Intercalation compound Metal metal oxide batteries Manganese oxides Organic electrolyte storage battery Spinels Electrodissolution Lithium oxide |
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| References | Blyr, Sigala, Amatucci, Guyomard, Chabre, Tarascon (BIB4) 1998; 145 Thackeray, Rossouw, Gummow, Liles, Pearce, De Kock, David, Hull (BIB6) 1993; 38 P. Arara, R.E. White, M. Doyle, J. Electrochem. Soc. 145 (1998) 3647 and references therein. A. Du Pasquier, A. Blyr, P. Courjal, D. Larcher, G. Amatucci, B. Gerand, J.-M. Tarascon, J. Electrochem. Soc. 146 (1999) 428 and references therein. Y. Wang, J. Reimers, IMLB, Edinburgh, 1998. H. Huang, C.A. Vincent, P.G. Bruce, J. Electrochem. Soc. 146 (1999) 481 and references therein. Xia, Zhou, Yoshio (BIB7) 1997; 144 Hunter (BIB3) 1981; 39 |
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| SubjectTerms | Applied sciences Capacity fade Direct energy conversion and energy accumulation Electrical engineering. Electrical power engineering Electrical power engineering Electrochemical conversion: primary and secondary batteries, fuel cells Exact sciences and technology Lithium manganese oxides Mn dissolution Storage |
| Title | Mechanisms of manganese spinels dissolution and capacity fade at high temperature |
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