Phase Compatible NiFe2O4 Coating Tunes Oxygen Redox in Li-Rich Layered Oxide

Jiming Peng; Yu Li; Zhiqiang Chen; Gemeng Liang; Sijiang Hu; Tengfei Zhou; Fenghua Zheng; Qichang Pan; Hongqiang Wang; Qingyu Li; Jianwen Liu; Zaiping Guo

doi:10.1021/acsnano.1c02023

Phase Compatible NiFe₂O₄Coating Tunes Oxygen Redox in Li-Rich Layered Oxide

Jiming Peng (Co-first Author)
, Yu Li (Co-first Author)
, Zhiqiang Chen
, Gemeng Liang
, Sijiang Hu^*
, Tengfei Zhou
, Fenghua Zheng
, Qichang Pan
, Hongqiang Wang^*
, Qingyu Li
, Jianwen Liu
, Zaiping Guo^*

^*Corresponding author for this work

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

172 Citations (Scopus)

Abstract

Li-rich layered oxides have attracted intense attention for lithium-ion batteries, as provide substantial capacity from transition metal cation redox simultaneous with reversible oxygen-anion redox. However, unregulated irreversible oxygen-anion redox leads to critical issues such as voltage fade and oxygen release. Here, we report a feasible NiFe₂O₄ (NFO) surface-coating strategy to turn the nonbonding coordination of surface oxygen into metal-oxygen decoordination. In particular, the surface simplex M-O (M = Ni, Co, Mn from MO₆ octahedra) and N-O (N = Ni, Fe from NO₆ octahedra) bonds are reconstructed in the form of M-O-N bonds. By applying both in operando and ex situ technologies, we found this heterostructural interface traps surface lattice oxygen, as well as restrains cation migration in Li-rich layered oxide during electrochemical cycling. Therefore, surface lattice oxygen behavior is significantly sustained. More interestingly, we directly observe the surface oxygen redox decouple with cation migration. In addition, the NFO-coating blocks HF produced from electrolyte decomposition, resulting in reducing the dissolution of Mn. With this strategy, higher cycle stability (91.8% at 1 C after 200 cycles) and higher rate capability (109.4 mA g^-1 at 1 C) were achieved in this work, compared with pristine Li-rich layered oxide. Our work offers potential for designing electrode materials utilizing oxygen redox chemistry. © 2021 American Chemical Society.

Original language	English
Pages (from-to)	11607-11618
Journal	ACS Nano
Volume	15
Issue number	7
Online published	24 Jun 2021
DOIs	https://doi.org/10.1021/acsnano.1c02023
Publication status	Published - 27 Jul 2021
Externally published	Yes

Funding

We acknowledge the support from the National Natural Science Foundation of China (Grant Nos. 51902108, 51762006, 51802357, and 51774100), Guangxi Technology Base and Talent Subject (Grant No. GUIKE AD20297086), Guangxi Innovation Driven Development Subject (Grant No. GUIKE AA19182020), Guangxi Natural Science Foundation (Grant No. 2018GXNSFBA138002), Guangxi Technology Base and Talent Subject (Grant No. GUIKE AD18126001), and Special Fund for Guangxi Distinguished Expert. G.M.L. acknowledges the Australian Institute of Nuclear Science and Engineering (AINSE) Limited for financial assistance in the form of a Post Graduate Research Award (PGRA).

UN SDGs

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

SDG 7 Affordable and Clean Energy

Research Keywords

Li-rich layered oxide
lithium-ion batteries
oxygen redox
surface coating
voltage fade

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10.1021/acsnano.1c02023

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Cite this

@article{a42c4274fd1547b1b79619d3fc39a4da,

title = "Phase Compatible NiFe2O4 Coating Tunes Oxygen Redox in Li-Rich Layered Oxide",

abstract = "Li-rich layered oxides have attracted intense attention for lithium-ion batteries, as provide substantial capacity from transition metal cation redox simultaneous with reversible oxygen-anion redox. However, unregulated irreversible oxygen-anion redox leads to critical issues such as voltage fade and oxygen release. Here, we report a feasible NiFe2O4 (NFO) surface-coating strategy to turn the nonbonding coordination of surface oxygen into metal-oxygen decoordination. In particular, the surface simplex M-O (M = Ni, Co, Mn from MO6 octahedra) and N-O (N = Ni, Fe from NO6 octahedra) bonds are reconstructed in the form of M-O-N bonds. By applying both in operando and ex situ technologies, we found this heterostructural interface traps surface lattice oxygen, as well as restrains cation migration in Li-rich layered oxide during electrochemical cycling. Therefore, surface lattice oxygen behavior is significantly sustained. More interestingly, we directly observe the surface oxygen redox decouple with cation migration. In addition, the NFO-coating blocks HF produced from electrolyte decomposition, resulting in reducing the dissolution of Mn. With this strategy, higher cycle stability (91.8\% at 1 C after 200 cycles) and higher rate capability (109.4 mA g-1 at 1 C) were achieved in this work, compared with pristine Li-rich layered oxide. Our work offers potential for designing electrode materials utilizing oxygen redox chemistry. {\textcopyright} 2021 American Chemical Society.",

keywords = "Li-rich layered oxide, lithium-ion batteries, oxygen redox, surface coating, voltage fade",

author = "Jiming Peng and Yu Li and Zhiqiang Chen and Gemeng Liang and Sijiang Hu and Tengfei Zhou and Fenghua Zheng and Qichang Pan and Hongqiang Wang and Qingyu Li and Jianwen Liu and Zaiping Guo",

year = "2021",

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doi = "10.1021/acsnano.1c02023",

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T1 - Phase Compatible NiFe2O4 Coating Tunes Oxygen Redox in Li-Rich Layered Oxide

AU - Peng, Jiming

AU - Li, Yu

AU - Chen, Zhiqiang

AU - Liang, Gemeng

AU - Hu, Sijiang

AU - Zhou, Tengfei

AU - Zheng, Fenghua

AU - Pan, Qichang

AU - Wang, Hongqiang

AU - Li, Qingyu

AU - Liu, Jianwen

AU - Guo, Zaiping

PY - 2021/7/27

Y1 - 2021/7/27

N2 - Li-rich layered oxides have attracted intense attention for lithium-ion batteries, as provide substantial capacity from transition metal cation redox simultaneous with reversible oxygen-anion redox. However, unregulated irreversible oxygen-anion redox leads to critical issues such as voltage fade and oxygen release. Here, we report a feasible NiFe2O4 (NFO) surface-coating strategy to turn the nonbonding coordination of surface oxygen into metal-oxygen decoordination. In particular, the surface simplex M-O (M = Ni, Co, Mn from MO6 octahedra) and N-O (N = Ni, Fe from NO6 octahedra) bonds are reconstructed in the form of M-O-N bonds. By applying both in operando and ex situ technologies, we found this heterostructural interface traps surface lattice oxygen, as well as restrains cation migration in Li-rich layered oxide during electrochemical cycling. Therefore, surface lattice oxygen behavior is significantly sustained. More interestingly, we directly observe the surface oxygen redox decouple with cation migration. In addition, the NFO-coating blocks HF produced from electrolyte decomposition, resulting in reducing the dissolution of Mn. With this strategy, higher cycle stability (91.8% at 1 C after 200 cycles) and higher rate capability (109.4 mA g-1 at 1 C) were achieved in this work, compared with pristine Li-rich layered oxide. Our work offers potential for designing electrode materials utilizing oxygen redox chemistry. © 2021 American Chemical Society.

AB - Li-rich layered oxides have attracted intense attention for lithium-ion batteries, as provide substantial capacity from transition metal cation redox simultaneous with reversible oxygen-anion redox. However, unregulated irreversible oxygen-anion redox leads to critical issues such as voltage fade and oxygen release. Here, we report a feasible NiFe2O4 (NFO) surface-coating strategy to turn the nonbonding coordination of surface oxygen into metal-oxygen decoordination. In particular, the surface simplex M-O (M = Ni, Co, Mn from MO6 octahedra) and N-O (N = Ni, Fe from NO6 octahedra) bonds are reconstructed in the form of M-O-N bonds. By applying both in operando and ex situ technologies, we found this heterostructural interface traps surface lattice oxygen, as well as restrains cation migration in Li-rich layered oxide during electrochemical cycling. Therefore, surface lattice oxygen behavior is significantly sustained. More interestingly, we directly observe the surface oxygen redox decouple with cation migration. In addition, the NFO-coating blocks HF produced from electrolyte decomposition, resulting in reducing the dissolution of Mn. With this strategy, higher cycle stability (91.8% at 1 C after 200 cycles) and higher rate capability (109.4 mA g-1 at 1 C) were achieved in this work, compared with pristine Li-rich layered oxide. Our work offers potential for designing electrode materials utilizing oxygen redox chemistry. © 2021 American Chemical Society.

KW - Li-rich layered oxide

KW - lithium-ion batteries

KW - oxygen redox

KW - surface coating

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