Ti<sup>4+</sup> doping coupled with zirconium nitrate solution quenching for synergistic modification of lithium-rich layered oxide cathodes

LI Jie; ZENG Hua; LIU Bo; LI Daoyu; NI Wei; YUAN Xinran; XIN Yanan

doi:10.7513/j.issn.1004-7638.2026.03.007

Volume 47 Issue 3

Jun. 2026

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LI Jie, ZENG Hua, LIU Bo, LI Daoyu, NI Wei, YUAN Xinran, XIN Yanan. Ti4+ doping coupled with zirconium nitrate solution quenching for synergistic modification of lithium-rich layered oxide cathodes[J]. IRON STEEL VANADIUM TITANIUM, 2026, 47(3): 63-72. doi: 10.7513/j.issn.1004-7638.2026.03.007

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LI Jie, ZENG Hua, LIU Bo, LI Daoyu, NI Wei, YUAN Xinran, XIN Yanan. Ti⁴⁺ doping coupled with zirconium nitrate solution quenching for synergistic modification of lithium-rich layered oxide cathodes[J]. IRON STEEL VANADIUM TITANIUM, 2026, 47(3): 63-72. doi: 10.7513/j.issn.1004-7638.2026.03.007

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Ti⁴⁺ doping coupled with zirconium nitrate solution quenching for synergistic modification of lithium-rich layered oxide cathodes

doi: 10.7513/j.issn.1004-7638.2026.03.007

LI Jie^{1, 2
,},
ZENG Hua²,
LIU Bo²,
LI Daoyu¹,
NI Wei²,
YUAN Xinran³,
XIN Yanan^{1, 2
,
,}

1.
Sichuan Provincial Key Laboratory for High-Value Utilization of Vanadium and Titanium Resources, Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd., Panzhihua 617000, Sichuan, China
2.
Department of Advanced Functional Materials, Chengdu Institute of Advanced Metallic Materials Technology and Industry Co., Ltd., Chengdu 610300, Sichuan, China
3.
Beijing Vanadium-Titanium Research Branch, Panzhihua Steel Group Research Institute Co., Ltd, Beijing 102211, China

More Information

Received Date: 2026-01-13
Accepted Date: 2026-02-09
Rev Recd Date: 2026-01-27
Publish Date: 2026-06-29

Abstract

Abstract

Lithium-rich layered oxides (LLOs) are the most promising next-generation cathode materials for lithium-ion batteries. However, the performance degradation triggered by their bulk-surface dual deterioration severely hinders commercial application. Herein, a synergistic modification strategy of bulk Ti⁴⁺ doping and zirconium nitrate solution quenching is proposed to construct a dual stabilization system of “bulk strengthening-surface protection.” Ti⁴⁺ substitutes Mn sites in the bulk, significantly inhibiting lattice oxygen release, transition metal (TM) ion migration, and irreversible structural phase transition via strong Ti-O bonds; solution quenching enables rapid ion exchange and in-situ structural reconstruction, forming a Zr-based multifunctional layer with Zr⁴⁺ doping and a disordered rock-salt shell on the particle surface, which functions as interfacial isolation, lattice oxygen stabilization and Li⁺ diffusion channel expansion. The results demonstrate that the structural stability and electrochemical performance of TZ-LNMO are remarkably enhanced. Specifically, it delivers a reversible specific capacity of 271.8 mAh/g with an Initial Coulombic efficiency (ICE) of 85.21% at 0.1C. After 300 cycles at 1C, the capacity retention reaches up to 90.8% with a small voltage fading rate of 0.56 mV per cycle.
- lithium-rich layered oxides,
- Ti⁴⁺ doping,
- solution quenching,
- disordered rock salt structure

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References(30)

References

[1]	ASSAT G, TARASCON J-M. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries[J]. Nature Energy, 2018, 3(5): 373-386. doi: 10.1038/s41560-018-0097-0
[2]	ZUO W, LUO M, LIU X, et al. Li-rich cathodes for rechargeable Li-based batteries: reaction mechanisms and advanced characterization techniques[J]. Energy & Environmental Science, 2020, 13(12): 4450-4497. doi: 10.1039/D0EE01694B
[3]	YU H, ISHIKAWA R, SO Y G, et al. Direct atomic-resolution observation of two phases in the Li_1.2Mn_0.567Ni_0.166Co_0.067O₂ cathode material for lithium-ion batteries[J]. Angewandte Chemie International Edition, 2013, 52(23): 5969-5973.
[4]	SEO D H, LEE J, URBAN A, et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials[J]. Nature Chemistry, 2016, 8(7): 692-697. doi: 10.1038/nchem.2524
[5]	RAMAKRISHNAN S, PARK B, WU J, et al. Extended interfacial stability through simple acid rinsing in a Li-rich oxide cathode material[J]. Journal of the American Chemical Society, 2020, 142(18): 8522-8531. doi: 10.1021/jacs.0c02859
[6]	YU W H, ZHAO L Y, WANG Y Y, et al. Challenges and solutions of lithium-rich manganese-based cathode materials for lithium-ion batteries[J]. Journal of the Chinese Ceramic Society, 2022, 50(11): 3040-3060. (于文华, 赵刘洋, 王艳艳, 等. 锂离子电池富锂锰基正极材料面临的挑战及解决方案[J]. 硅酸盐学报, 2022, 50(11): 3040-3060. doi: 10.14062/j.issn.0454-5648.20220251 YU W H, ZHAO L Y, WANG Y Y, et al. Challenges and solutions of lithium-rich manganese-based cathode materials for lithium-ion batteries[J]. Journal of the Chinese Ceramic Society, 2022, 50（11）: 3040-3060. doi: 10.14062/j.issn.0454-5648.20220251
[7]	HOUSE R A, MARIE J-J, PÉREZ-OSORIO M A, et al. The role of O₂ in O-redox cathodes for Li-ion batteries[J]. Nature Energy, 2021, 6(8): 781-789. doi: 10.1038/s41560-021-00780-2
[8]	LI B, XIA D. Anionic redox in rechargeable lithium batteries[J]. Advanced Materials, 2017, 29(48): 1701054. doi: 10.1002/adma.201701054
[9]	HOUSE R A, REES G J, PÉREZ-OSORIO M A, et al. First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O₂ trapped in the bulk[J]. Nature Energy, 2020, 5(10): 777-785. doi: 10.1038/s41560-020-00697-2
[10]	YU Z, SHANG S-L, GORDIN M L, et al. Ti-substituted Li[Li_0.26Mn_0.6−xTi_xNi_0.07Co_0.07]O₂ layered cathode material with improved structural stability and suppressed voltage fading[J]. Journal of Materials Chemistry A, 2015, 3(33): 17376-17384.
[11]	FENG X, GAO Y, BEN L, et al. Enhanced electrochemical performance of Ti-doped Li_1.2Mn_0.54Co_0.13Ni_0.13O₂ for lithium-ion batteries[J]. Journal of Power Sources, 2016, 317: 74-80. doi: 10.1016/j.jpowsour.2016.03.101
[12]	YAMAMOTO S, NOGUCHI H, ZHAO W W. Improvement of cycling performance in Ti substituted 0.5Li₂MnO₃-0.5LiNi_0.5Mn_0.5O₂ through suppressing metal dissolution[J]. Journal of Power Sources, 2015, 278: 76-86. doi: 10.1016/j.jpowsour.2014.12.038
[13]	DING X, LI Y X, CHEN F, et al. In situ formation of LiF decoration on a Li-rich material for long-cycle life and superb low-temperature performance[J]. Journal of Materials Chemistry A, 2019, 7(18): 11513-11519. doi: 10.1039/C9TA02461A
[14]	LIU S, LIU Z, SHEN X, et al. Surface doping to enhance structural integrity and performance of Li‐rich layered oxide[J]. Advanced Energy Materials, 2018, 8(31): 1802105. doi: 10.1002/aenm.201802105
[15]	ZHU Z, YU D, YANG Y, et al. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment[J]. Nature Energy, 2019, 4(12): 1049-1058. doi: 10.1038/s41560-019-0508-x
[16]	LI Z L, FAN M, CHU J T, et al. Enhanced electrochemical performance of lithium-rich manganese-based cathode materials through surface modification with sodium borohydride[J]. Journal of Xi'an Technological University, 2025, 45(3): 382-394. (李政隆, 范淼, 褚静婷, 等. NaBH₄表面改性富锂锰基正极材料性能研究[J]. 西安工业大学学报, 2025, 45(3): 382-394. LI Z L, FAN M, CHU J T, et al. Enhanced electrochemical performance of lithium-rich manganese-based cathode materials through surface modification with sodium borohydride[J]. Journal of Xi'an Technological University, 2025, 45（3）: 382-394.
[17]	KANG G H, LIU X X, ZHANG L Y, et al. Enhances electrochemical performance of lithium-rich manganese-based cathode material Li_1.2Mn_0.54Co_0.13Ni_0.13O₂ via Li₃InCl₆ coating modification[J]. China's Manganese Industry, 2025, 43(4): 1-7. (康国辉, 刘鑫翔, 张丽云, 等. Li₃InCl₆包覆改性提升富锂锰基正极材料Li_1.2Mn_0.54Co_0.13Ni_0.13O₂的电化学性能[J]. 中国锰业, 2025, 43(4): 1-7. doi: 10.14101/j.cnki.issn.1002-4336.2025.04.008 KANG G H, LIU X X, ZHANG L Y, et al. Enhances electrochemical performance of lithium-rich manganese-based cathode material Li_1.2Mn_0.54Co_0.13Ni_0.13O₂ via Li₃InCl₆ coating modification[J]. China's Manganese Industry, 2025, 43（4）: 1-7. doi: 10.14101/j.cnki.issn.1002-4336.2025.04.008
[18]	YE C C, LIU J Z, ZHANG Q H, et al. Activating metal oxides nanocatalysts for electrocatalytic water oxidation by quenching-induced near-surface metal atom functionality[J]. Journal of the American Chemical Society, 2021, 143(35): 14169-14177. doi: 10.1021/jacs.1c04737
[19]	LIU Z P, LIU S, YANG L, et al. Feasibility to improve the stability of lithium-rich layered oxides by surface doping[J]. ACS Applied Materials & Interfaces, 2022, 14(16): 18353-18359. doi: 10.1021/acsami.2c00155
[20]	GAO S, ZHAN X W, CHENG Y T. Structural, electrochemical and Li-ion transport properties of Zr-modified LiNi_0.8Co_0.1Mn_0.1O₂ positive electrode materials for Li-ion batteries[J]. Journal of Power Sources, 2019, 410: 45-52.
[21]	LI J, ZHANG Y, GUO X, et al. Multifunctional surface-integrated structures enabling layered oxide cathodes with stable high-voltage cycling[J]. ACS Energy Letters, 2024, 9(9): 4339-4346. doi: 10.1021/acsenergylett.4c01719
[22]	CHENG X, WEI H, HAO W, et al. A cobalt-free Li(Li_0.16Ni_0.19Fe_0.18Mn_0.46)O₂ cathode for lithium-ion batteries with anionic redox reactions[J]. Chem Sus Chem, 2019, 12(6): 1162-1168.
[23]	SHAJU K M, RAO G V S, CHOWDARI B V R. Performance of layered Li(Ni_1/3Co_1/3Mn_1/3)O₂ as cathode for Li-ion batteries[J]. Electrochimica Acta, 2002, 48(2): 145-151. doi: 10.1016/S0013-4686(02)00593-5
[24]	LI G, REN Z, LI A, et al. Highly stable surface and structural origin for lithium-rich layered oxide cathode materials[J]. Nano Energy, 2022, 98: 107169. doi: 10.1016/j.nanoen.2022.107169
[25]	YU Y M, LIU J J, QI R, et al. Interface-reconstruction forming bifunctional (Li_xTM_1-x)O rock-salt shell for enhanced cyclability in Li-rich layered oxide[J]. Chinese Journal of Structure Chemistry, 2020, 39(8): 1363-1371.
[26]	THACKERAY M M, KANG S H, JOHNSON C S, et al. Li₂MnO₃-stabilized LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries[J]. Journal of Materials Chemistry, 2007, 17(30): 3112-3125. doi: 10.1039/b702425h
[27]	YU Z, NING F H, LI B, et al. Mitigating voltage decay of Li-rich layered oxide by incorporation of 5d metal rhenium[J]. Journal of Physical Chemistry C, 2019, 123(31): 18870-18876. doi: 10.1021/acs.jpcc.9b05683
[28]	LI Z B, LI Y W, ZHANG M J, et al. Modifying Li@Mn₆ superstructure units by Al substitution to enhance the long-cycle performance of Co-free Li-rich cathode[J]. Advanced Energy Materials, 2021, 11(37): 2101962. doi: 10.1002/aenm.202101962
[29]	GAO Y E, LI G, DU Z X, et al. Synthesis of high-performance Al-doped Li-rich manganese-based cathode materials via two-step calcination[J]. Chinese Journal of Power Sources, 2023, 47(12): 1549-1554. (高永恩, 李刚, 杜泽学, 等. 两步煅烧制备高性能Al掺杂富锂锰基正极材料[J]. 电源技术, 2023, 47(12): 1549-1554. GAO Y E, LI G, DU Z X, et al. Synthesis of high-performance Al-doped Li-rich manganese-based cathode materials via two-step calcination[J]. Chinese Journal of Power Sources, 2023, 47（12）: 1549-1554.
[30]	ZHAO H, LI W, LI J, et al. Enhance performances of Co-free Li-rich cathode by eutesctic melting salt treatment[J]. Nano Energy, 2022, 92: 106760. doi: 10.1016/j.nanoen.2021.106760