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Charging Mechanism of Li2MnO3
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- Guerrini, Niccolo (author)
- Dyson Technol Ltd, Malmesbury SN16 0RP, England.
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- Jin, Liyu (author)
- Dyson Technol Ltd, Malmesbury SN16 0RP, England.
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- Lozano, Juan G. (author)
- Univ Oxford, Dept Mat, Oxford OX1 3PH, England.;Univ Oxford, Dept Chem, Oxford OX1 3PH, England.
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- Dyson Technol Ltd, Malmesbury SN16 0RP, England Univ Oxford, Dept Mat, Oxford OX1 3PH, England.;Univ Oxford, Dept Chem, Oxford OX1 3PH, England. (creator_code:org_t)
- 2020-04-14
- 2020
- English.
- In: Chemistry of Materials. - : AMER CHEMICAL SOC. - 0897-4756 .- 1520-5002. ; 32:9, s. 3733-3740
- Journal article (peer-reviewed)
Abstract
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- Operando mass spectroscopy demonstrates quantitatively that lithium extraction from Li2MnO3 is charge compensated by oxygen loss (O-loss) not oxidation of oxide ions that are retained within the structural framework (O-redox). This fact is confirmed by X-ray absorption and emission spectroscopy. Li NMR shows that the two-phase core-shell structure, which forms on charging, is composed of an intact Li2MnO3 core and a highly disordered shell containing no Li, with a composition close to MnO2. Discharge involves Li insertion into the disordered shell. CO2 and O-2 are detected on charging at 15 mA g(-1), whereas charging by galvanostatic intermittent titration technique (GITT) forms only CO2; an observation in agreement with the previously described model of oxygen evolution from high-voltage cathodes producing singlet O-2 that reacts with the electrolyte forming CO2. The dominance of oxygen evolution over O-redox is in accordance with the model of O-loss occurring when the oxide ions are undercoordinated; O in the shell devoid of Li is coordinated by only 2 Mn.
Subject headings
- NATURVETENSKAP -- Kemi -- Materialkemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Materials Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
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