Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries

Gemeng Liang; Emilia Olsson; Jinshuo Zou; Zhibin Wu; Jingxi Li; Cheng-Zhang Lu; Anita M. D'Angelo; Bernt Johannessen; Lars Thomsen; Bruce Cowie; Vanessa K. Peterson; Qiong Cai; Wei Kong Pang; Zaiping Guo

doi:10.1002/anie.202201969

Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries

Gemeng Liang, Emilia Olsson, Jinshuo Zou, Zhibin Wu, Jingxi Li, Cheng-Zhang Lu, Anita M. D'Angelo, Bernt Johannessen, Lars Thomsen, Bruce Cowie, Vanessa K. Peterson, Qiong Cai, Wei Kong Pang^*, Zaiping Guo^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

60 Citations (Scopus)

1 Downloads (CityUHK Scholars)

Abstract

Oxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium-ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3d–2p interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4s–2p orbital hybridization into the structure using LiNi_0.5Mn_1.5O₄ oxide as an example. The modified oxide delivers extraordinarily stable battery performance, achieving 71.4 % capacity retention after 2000 cycles at 1 C. This work shows that an orbital-level understanding can be leveraged to engineer high structural stability of the anion oxygen framework of oxides. Moreover, the similarity of the oxygen lattice between oxide electrodes makes this approach extendable to other electrodes, with orbital-focused engineering a new avenue for the fundamental modification of battery materials. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Original language	English
Article number	e202201969
Number of pages	11
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	27
Online published	25 Apr 2022
DOIs	https://doi.org/10.1002/anie.202201969
Publication status	Published - 4 Jul 2022
Externally published	Yes

Funding

This work is supported by the Australian Research Council under grants FT160100251, DP200101862, DP210101486, and FL210100050. Dr. G. Liang thanks the Australian Institute of Nuclear Science and Engineering (AINSE) Limited for providing financial assistance in the form of a Post Graduate Research Award (PGRA). The authors acknowledge the operational support of ANSTO staff for neutron/synchrotron-based characterizations (Awarded beamtime: M16603, M16093, M14711, P9158). The support from Engineering and Physical Sciences Council (grant numbers EP/R021554/2, EP/L000202, EP/P020194 and EP/T022213) and University of Surrey Academic Disruption Fund are appreciated. Open access publishing facilitated by The University of Adelaide, as part of the Wiley - The University of Adelaide agreement via the Council of Australian University Librarians.

Research Keywords

4s–2p Orbital Hybridization
Lithium-Ion Batteries
Orbital Modification
Oxygen Framework
Spinel Oxides

Publisher's Copyright Statement

This full text is made available under CC-BY-NC-ND 4.0. https://creativecommons.org/licenses/by-nc-nd/4.0/

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access Output

10.1002/anie.202201969

297749455.pdfFinal Published version, 816 KBLicence: CC BY-NC-ND

Other Access Options

Check CityUHK Library

Permanent Link

Right click to copy link

Cite this

Liang, G., Olsson, E., Zou, J., Wu, Z., Li, J., Lu, C.-Z., D'Angelo, A. M., Johannessen, B., Thomsen, L., Cowie, B., Peterson, V. K., Cai, Q., Pang, W. K., & Guo, Z. (2022). Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries. Angewandte Chemie - International Edition, 61(27), Article e202201969. https://doi.org/10.1002/anie.202201969

@article{41af2be97d1e412dbba2f819098d3931,

title = "Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries",

abstract = "Oxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium-ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3d–2p interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4s–2p orbital hybridization into the structure using LiNi0.5Mn1.5O4 oxide as an example. The modified oxide delivers extraordinarily stable battery performance, achieving 71.4 % capacity retention after 2000 cycles at 1 C. This work shows that an orbital-level understanding can be leveraged to engineer high structural stability of the anion oxygen framework of oxides. Moreover, the similarity of the oxygen lattice between oxide electrodes makes this approach extendable to other electrodes, with orbital-focused engineering a new avenue for the fundamental modification of battery materials. {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

keywords = "4s–2p Orbital Hybridization, Lithium-Ion Batteries, Orbital Modification, Oxygen Framework, Spinel Oxides",

author = "Gemeng Liang and Emilia Olsson and Jinshuo Zou and Zhibin Wu and Jingxi Li and Cheng-Zhang Lu and D'Angelo, {Anita M.} and Bernt Johannessen and Lars Thomsen and Bruce Cowie and Peterson, {Vanessa K.} and Qiong Cai and Pang, {Wei Kong} and Zaiping Guo",

year = "2022",

month = jul,

day = "4",

doi = "10.1002/anie.202201969",

language = "English",

volume = "61",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons",

number = "27",

}

TY - JOUR

T1 - Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries

AU - Liang, Gemeng

AU - Olsson, Emilia

AU - Zou, Jinshuo

AU - Wu, Zhibin

AU - Li, Jingxi

AU - Lu, Cheng-Zhang

AU - D'Angelo, Anita M.

AU - Johannessen, Bernt

AU - Thomsen, Lars

AU - Cowie, Bruce

AU - Peterson, Vanessa K.

AU - Cai, Qiong

AU - Pang, Wei Kong

AU - Guo, Zaiping

PY - 2022/7/4

Y1 - 2022/7/4

N2 - Oxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium-ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3d–2p interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4s–2p orbital hybridization into the structure using LiNi0.5Mn1.5O4 oxide as an example. The modified oxide delivers extraordinarily stable battery performance, achieving 71.4 % capacity retention after 2000 cycles at 1 C. This work shows that an orbital-level understanding can be leveraged to engineer high structural stability of the anion oxygen framework of oxides. Moreover, the similarity of the oxygen lattice between oxide electrodes makes this approach extendable to other electrodes, with orbital-focused engineering a new avenue for the fundamental modification of battery materials. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

AB - Oxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium-ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3d–2p interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4s–2p orbital hybridization into the structure using LiNi0.5Mn1.5O4 oxide as an example. The modified oxide delivers extraordinarily stable battery performance, achieving 71.4 % capacity retention after 2000 cycles at 1 C. This work shows that an orbital-level understanding can be leveraged to engineer high structural stability of the anion oxygen framework of oxides. Moreover, the similarity of the oxygen lattice between oxide electrodes makes this approach extendable to other electrodes, with orbital-focused engineering a new avenue for the fundamental modification of battery materials. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

KW - 4s–2p Orbital Hybridization

KW - Lithium-Ion Batteries

KW - Orbital Modification

KW - Oxygen Framework

KW - Spinel Oxides

UR - http://www.scopus.com/inward/record.url?scp=85129378440&partnerID=8YFLogxK

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85129378440&origin=recordpage

U2 - 10.1002/anie.202201969

DO - 10.1002/anie.202201969

M3 - RGC 21 - Publication in refereed journal

C2 - 35467801

SN - 1433-7851

VL - 61

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 27

M1 - e202201969

ER -

Introducing 4s–2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries

Abstract

Funding

Research Keywords

Publisher's Copyright Statement

UN SDGs

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

Cite this