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Research Article

Stabilizing effects of atomic Ti doping on high-voltage high-nickel layered oxide cathode for lithium-ion rechargeable batteries

Yong Cheng1,2,§, Yan Sun3,§, Changting Chu1, Limin Chang1( ), Zhaomin Wang3, Dongyu Zhang2, Wanqiang Liu3( ), Zechao Zhuang4( ), Limin Wang1,2
Key Laboratory of Preparation and Applications of Environmental Friendly Materials (Ministry of Education), Jilin Normal University, Changchun 130103, China
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
School of materials science and engineering, Changchun University of Science and Technology, Changchun 130022, China
Department of Chemistry, Tsinghua University, Beijing 100084, China

§ Yong Cheng and Yan Sun contributed equally to this work.

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Graphical Abstract

The homogeneous Ti-doped high-voltage high-nickel lithium layered oxide cathode LiNi0.6Co0.2Mn0.18Ti0.02O2 (NCM-Ti) is successfully prepared through a liquid phase physical mixing and high-temperature annealing method. Ti doping inhibits the undesired H2-H3 phase transition, minimizing the mechanical degradation due to the strong Ti–O bond and no unpaired electrons for Ti4+, and Ti-doped NCM shows superior cycle stability and an energy density of up to 240 Wh·Kg−1.

Abstract

High-voltage high-nickel lithium layered oxide cathodes show great application prospects to meet the ever-increasing demand for further improvement of the energy density of rechargeable lithium-ion batteries (LIBs) mainly due to their high output capacity. However, severe bulk structural degradation and undesired electrode–electrolyte interface reactions seriously endanger the cycle life and safety of the battery. Here, 2 mol% Ti atom is used as modified material doping into LiNi0.6Co0.2Mn0.2O2 (NCM) to reform LiNi0.6Co0.2Mn0.18Ti0.02O2 (NCM-Ti) and address the long-standing inherent problem. At a high cut-off voltage of 4.5 V, NCM-Ti delivers a higher capacity retention ratio (91.8% vs. 82.9%) after 150 cycles and a superior rate capacity (118 vs. 105 mAh·g−1) at the high current density of 10 C than the pristine NCM. The designed high-voltage full battery with graphite as anode and NCM-Ti as cathode also exhibits high energy density (240 Wh·kg−1) and excellent electrochemical performance. The superior electrochemical behavior can be attributed to the improved stability of the bulk structure and the electrode–electrolyte interface owing to the strong Ti–O bond and no unpaired electrons. The in-situ X-ray diffraction analysis demonstrates that Ti-doping inhibits the undesired H2-H3 phase transition, minimizing the mechanical degradation. The ex-situ TEM and X-ray photoelectron spectroscopy reveal that Ti-doping suppresses the release of interfacial oxygen, reducing undesired interfacial reactions. This work provides a valuable strategic guideline for the application of high-voltage high-nickel cathodes in LIBs.

Keywords

lithium-ion batteryhigh-voltage high-nickel cathodeTi-dopingstructural stabilityinterface stability

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Nano Research
Volume 15 Issue 5,
May 2022
Pages 4091-4099
DOI: 10.1007/s12274-021-4035-2
Cite this article:
Cheng Y, Sun Y, Chu C, et al. Stabilizing effects of atomic Ti doping on high-voltage high-nickel layered oxide cathode for lithium-ion rechargeable batteries. Nano Research, 2022, 15(5): 4091-4099. https://doi.org/10.1007/s12274-021-4035-2
Topics:
Lithium batteries

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Received: 03 November 2021
Revised: 29 November 2021
Accepted: 30 November 2021
Published: 18 January 2022
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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