Journal
JOURNAL OF MATERIALS CHEMISTRY A
Volume 6, Issue 28, Pages 13943-13951Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c8ta03667e
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Funding
- JSPS KAKENHI Grant [18H02076]
- MEXT program Elements Strategy Initiative to Form Core Research Center, MEXT
- Ministry of Education Culture, Sports, Science and Technology, Japan
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Stoichiometric LiMnO2 and NaMnO2 with a cation-disordered rocksalt-type structure as metastable polymorphs were successfully prepared by mechanical milling. Although cation-disordered rocksalt phases with a stoichiometric composition (Li:Mn molar ratio = 1:1) are expected to be electrochemically less active, both samples show superior performance as electrode materials when compared with thermodynamically stable layered phases in Li/Na cells. Both metastable samples deliver large reversible capacities, which correspond to >80% of their theoretical capacities, with relatively small polarization on the basis of reversible Mn3+/Mn4+ redox. Moreover, for rocksalt LiMnO2, the phase transition into a spinel phase is effectively suppressed compared with a thermodynamically stable phase. The electrode reversibility of NaMnO2 is also drastically improved by the use of the metastable phase with good capacity retention. Metastable phases with unique nanostructures open a new path for the design of advanced electrode materials with high energy density, and thus a broad impact is anticipated for rechargeable Li/Na battery applications.
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