TY - JOUR
T1 - Lattice Oxygen Instability in Oxide-Based Intercalation Cathodes
T2 - A Case Study of Layered LiNi1/3Co1/3Mn1/3O2
AU - Hou, Xueyan
AU - Ohta, Kento
AU - Kimura, Yuta
AU - Tamenori, Yusuke
AU - Tsuruta, Kazuki
AU - Amezawa, Koji
AU - Nakamura, Takashi
N1 - Funding Information:
This work was financially supported by JSPS KAKENHI Grant Nos. JP18K05288 and JP19H05814, the Research Program for CORE lab of “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” in “Network Joint Research Center for Materials and Devices,” and JACI Prize for Encouraging Young Researcher. The synchrotron radiation experiments were performed at BL01B1 and BL27SU of SPring‐8 with the approval of JASRI (Proposal Nos. 2019B1441, 2019B1450, and 2020A1713).
Funding Information:
This work was financially supported by JSPS KAKENHI Grant Nos. JP18K05288 and JP19H05814, the Research Program for CORE lab of ?Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials? in ?Network Joint Research Center for Materials and Devices,? and JACI Prize for Encouraging Young Researcher. The synchrotron radiation experiments were performed at BL01B1 and BL27SU of SPring-8 with the approval of JASRI (Proposal Nos. 2019B1441, 2019B1450, and 2020A1713).
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/8/12
Y1 - 2021/8/12
N2 - Oxide-based cathode materials are key components of secondary batteries, for example, alkali metal-ion and anion batteries, sufficient stability of which is thus vital for ensuring high energy density and safety. However, problems originating from the lattice oxygen instability in oxide-based intercalation cathodes are widely reported, such as capacity degradation, gas generation, and thermal runaway, highlighting the importance of deep insights into the critical factors for lattice oxygen stability. In this work, lattice oxygen stability in layered rock-salt LiNi1/3Co1/3Mn1/3O2−δ is investigated with a focus on oxygen release behavior and relevant changes in crystal and electronic structures. Release of lattice oxygen facilitates cation mixing, transition metal slab expansion, and Li slab contraction, thus deteriorating the layered structure. As is revealed by X-ray absorption spectroscopy, in the beginning stage of oxygen release, the charge balance is compensated by selective reduction of Ni3+. This strongly suggests that high valent Ni generated by delithiation or negative defect species, that is, lithium at the transition metal site ((Formula presented.) TM), aggravates oxygen release severely. The findings of this work provide a new research direction and guidelines for the stabilization of lattice oxygen in oxide-based intercalation cathodes.
AB - Oxide-based cathode materials are key components of secondary batteries, for example, alkali metal-ion and anion batteries, sufficient stability of which is thus vital for ensuring high energy density and safety. However, problems originating from the lattice oxygen instability in oxide-based intercalation cathodes are widely reported, such as capacity degradation, gas generation, and thermal runaway, highlighting the importance of deep insights into the critical factors for lattice oxygen stability. In this work, lattice oxygen stability in layered rock-salt LiNi1/3Co1/3Mn1/3O2−δ is investigated with a focus on oxygen release behavior and relevant changes in crystal and electronic structures. Release of lattice oxygen facilitates cation mixing, transition metal slab expansion, and Li slab contraction, thus deteriorating the layered structure. As is revealed by X-ray absorption spectroscopy, in the beginning stage of oxygen release, the charge balance is compensated by selective reduction of Ni3+. This strongly suggests that high valent Ni generated by delithiation or negative defect species, that is, lithium at the transition metal site ((Formula presented.) TM), aggravates oxygen release severely. The findings of this work provide a new research direction and guidelines for the stabilization of lattice oxygen in oxide-based intercalation cathodes.
KW - gas generation
KW - intercalation cathodes
KW - lattice oxygen instability
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U2 - 10.1002/aenm.202101005
DO - 10.1002/aenm.202101005
M3 - Article
AN - SCOPUS:85108338178
VL - 11
JO - Advanced Energy Materials
JF - Advanced Energy Materials
SN - 1614-6832
IS - 30
M1 - 2101005
ER -
