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 · Tue Nov 18 00:00:00 EST 2014 · Nature Communications

DOI:https://doi.org/10.1038/ncomms6381· OSTI ID:1169025

Zhou, Yong-Ning ^[1]; Ma, Jun ^[2]; Hu, Enyuan ^[1]; Yu, Xiqian ^[1]; Gu, Lin ^[2]; Nam, Kyung -Wan ^[3]; Chen, Liquan ^[2]; Wang, Zhaoxiang ^[2]; Yang, Xiao -Qing ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics (BNLCP-CAS)
Dongguk Univ., Seoul (Korea, Republic of)

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

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC00112704

OSTI ID:: 1169025

Report Number(s):: BNL-107086-2014-JA; BNL-107086-2014-JAAM; R&D Project: EST431; KC0207010

Journal Information:: Nature Communications, Journal Name: Nature Communications; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 169 works

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