Tuning charge-discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan; Yu, Xiqian; Gu, Lin; Nam, Kyung-Wan; Chen, Liquan; Wang, Zhaoxiang; Yang, Xiao-Qing

doi:10.1038/ncomms6381

Title: Tuning charge-discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

Journal Article · Thu Dec 18 00:00:00 EST 2014 · Nat. Commun.

DOI:https://doi.org/10.1038/ncomms6381· OSTI ID:1168481

Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan; Yu, Xiqian; Gu, Lin; Nam, Kyung-Wan; Chen, Liquan; Wang, Zhaoxiang; Yang, Xiao-Qing ^[1]

For LiMO₂ (M=Co, Ni, Mn) cathode materials, lattice parameters, a(b), contract during charge. Here we report such changes in opposite directions for lithium molybdenum trioxide (Li₂MoO₃). A ‘unit cell breathing’ mechanism is proposed based on crystal and electronic structural changes of transition metal oxides during charge-discharge. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of the metal-metal bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking metal-oxygen bond as controlling factor in ‘normal’ materials. The cation mixing caused by migration of molybdenum ions at higher oxidation state provides the benefits of reducing the c expansion range in the early stage of charging and suppressing the structure collapse at high voltage charge. These results may open a new strategy for designing layered cathode materials for high energy density lithium-ion batteries.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: DOE - NUCLEAR ENERGYFOREIGN

OSTI ID:: 1168481

Journal Information:: Nat. Commun., Vol. 5, Issue 2014

Country of Publication:: United States

Language:: ENGLISH

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