Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li2Mn4O9

Palos, A. Ibarra; Anne, M.; Strobel, Pierre

doi:10.1006/jssc.2001.9200

Cited by 24 publications

(4 citation statements)

References 16 publications

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“…(ii) Mn-OH formation. Protonation during cycling and formation of a -OH hydroxyl group has previously reported for spinel electrodes 44 and Li 2 MnO 3 . Charge compensation via the formation of hydroxyl groups would lead to the formation of H 1.5 Li 0.5 MnO 3 aer the rst charge to 4.5 V, giving rise to equal numbers of Mn-O and Mn-OH bonds.…”

Section: Evaluating Possible Charge Compensation Mechanismsmentioning

confidence: 65%

Reversible densification in nano-Li₂MnO₃ cation disordered rock-salt Li-ion battery cathodes

et al. 2020

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Section: Evaluating Possible Charge Compensation Mechanismsmentioning

confidence: 65%

Reversible densification in nano-Li₂MnO₃ cation disordered rock-salt Li-ion battery cathodes

et al. 2020

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“…This was explained by creating vacancies both at the 8a and 16d sites with decreasing synthesis temperatures. 18,20 However, our neutron refinement results indicated no vacancies at these sites. The lattice parameter also decreases with increasing x in Li 1 1 x Mn 2 2 x O 4 for both the 900 and 750 uC series, which was explained by the lithium substitution at the manganese 16d site.…”

Section: Structure Description Of the Spinelmentioning

confidence: 67%

Synthesis, structure, and phase relationship in lithium manganese oxide spinelElectronic supplementary information (ESI) available: neutron and X-ray Rietveld refinement results of LiMn2O4. See http://www.rsc.org/suppdata/jm/b3/b314810f/

et al. 2004

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Phase relationships, structures, magnetic properties, and phase transitions in the lithium manganese oxide spinel were studied based on a wide variety of samples synthesized at temperatures over a range of 750 ¡ t ¡ 900 uC with Li/Mn ratios between 0.5 and 0.55 and various starting materials. The system was divided into three categories: oxygen deficient spinels, LiMn 2 O 4 2 d ; lithium-substituted spinels, Li 1 1 x Mn 2 2 x O 4 2 d ; and the stoichiometric spinel, LiMn 2 O 4 . Their structures were discussed based on the structure data determined by TOF neutron and synchrotron X-ray Rietveld analysis. The amount of oxygen vacancy was determined to be d # 0.14(3) in LiMn 2 O 4 2 d , for example, for the spinel synthesized at 900 uC, and the nearly stoichiometric composition was obtained at 750 uC followed by heating at 470 uC for several times from lithium hydroxide and manganese oxides as starting materials. The oxygen vacancy was dependent upon the synthesis conditions and starting materials. It decreased as the Li/Mn ratio varied from 0.5 to 0.55, and as the synthesis temperature decreased from 900 to 750 uC. Based on the synthesis and structure results, the phase relationship in the ternary diagram, Li-Mn-O, is discussed.{ Electronic supplementary information (ESI) available: neutron and X-ray Rietveld refinement results of LiMn 2 O 4 . See

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“…The first one assumes the ideal formula, Li 4 Mn 5 O 12 , where the increased amount of manganese +4 is compensated by an excessive number of lithium ions at octahedral sites . The second model was built by introducing vacancies in the cation sublattice as described by the formula Li 2 Mn 4 O 9 (or alternatively Li 8/9 □ 1/9 [Mn 16/9 □ 2/9 ]O 4 , where □ denotes vacancy). , In the real structure, any mixture of these two ideal models is possible; a further level of complexity can be achieved by existence of Mn 3+ ion in less oxidizing conditions …”

Section: Introductionmentioning

confidence: 99%

Unusual Compressional Behavior of Lithium–Manganese Oxides: A Case Study of Li₄Mn₅O₁₂

2012

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Lithium-rich spinel oxide has been synthesized in a long-term low temperature sintering process via the intermediate defected phase. Synchrotron X-ray diffraction studies under pressure have been performed on Li4Mn5O12, and some similarity of its behavior under compression to that of LiMn2O4 has been demonstrated. Li4Mn5O12 reveals a bulk modulus value of K 0 = 118(1) GPa, and K 0′ = 4.5(3) GPa. This value is far below 200 GPa, which is typical of most spinel oxides. The local compressibility of LiO4 tetrahedra is responsible for these unusual elastic properties of lithium–manganese spinel oxides both with Mn4+ only and Mn3+/Mn4+ ions in octahedral sites.

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Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li2Mn4O9

Cited by 24 publications

References 16 publications

Reversible densification in nano-Li₂MnO₃ cation disordered rock-salt Li-ion battery cathodes

Reversible densification in nano-Li₂MnO₃ cation disordered rock-salt Li-ion battery cathodes

Synthesis, structure, and phase relationship in lithium manganese oxide spinelElectronic supplementary information (ESI) available: neutron and X-ray Rietveld refinement results of LiMn2O4. See http://www.rsc.org/suppdata/jm/b3/b314810f/

Unusual Compressional Behavior of Lithium–Manganese Oxides: A Case Study of Li₄Mn₅O₁₂

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Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li2Mn4O9

Cited by 24 publications

References 16 publications

Reversible densification in nano-Li2MnO3 cation disordered rock-salt Li-ion battery cathodes

Reversible densification in nano-Li2MnO3 cation disordered rock-salt Li-ion battery cathodes

Synthesis, structure, and phase relationship in lithium manganese oxide spinelElectronic supplementary information (ESI) available: neutron and X-ray Rietveld refinement results of LiMn2O4. See http://www.rsc.org/suppdata/jm/b3/b314810f/

Unusual Compressional Behavior of Lithium–Manganese Oxides: A Case Study of Li4Mn5O12

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Reversible densification in nano-Li₂MnO₃ cation disordered rock-salt Li-ion battery cathodes

Reversible densification in nano-Li₂MnO₃ cation disordered rock-salt Li-ion battery cathodes

Unusual Compressional Behavior of Lithium–Manganese Oxides: A Case Study of Li₄Mn₅O₁₂