有机-无机双层包覆协同优化LiNi0.5Mn1.5O4高压正极材料的界面及电化学性能

刘婧珺; 王博同; 刘海龙; 樊泽彤

doi:10.19799/j.cnki.2095-4239.2026.0634

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有机-无机双层包覆协同优化LiNi_0.5Mn_1.5O₄高压正极材料的界面及电化学性能

储能材料与器件 | 更新时间：2026-09-18

- 有机-无机双层包覆协同优化LiNi_0.5Mn_1.5O₄高压正极材料的界面及电化学性能
- Synergistic optimization of interface and electrochemical properties of LNMO high-voltage cathode material via organic-inorganic double-layer coating
- 储能科学与技术 2026年15卷第9期页码：3462-3475
- 作者机构：
  
  太原工业学院，山西太原 030008
- 作者简介：
  
  刘婧珺（1994—），女，博士，讲师，研究方向为锂离子电池正极材料，E-mail：liujing_jun@163.com。
- 基金信息：
  
  太原工业学院引进人才科研资助项目-博士（后）科研资助项目(2024KJ037);太原工业学院引进人才科研资助项目-来晋工作优秀博士（后）科研资助项目(2025LJ006)
- DOI：10.19799/j.cnki.2095-4239.2026.0634
  中图分类号： TM 911
- 收稿：2026-07-23，
  
  修回：2026-08-14，
  
  纸质出版：2026-09-28
- 稿件说明：
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刘婧珺, 王博同, 刘海龙, 等. 有机-无机双层包覆协同优化LiNi_0.5Mn_1.5O₄高压正极材料的界面及电化学性能[J]. 储能科学与技术, 2026, 15(9): 3462-3475. DOI: 10.19799/j.cnki.2095-4239.2026.0634.

LIU Jingjun, WANG Botong, LIU Hailong, et al. Synergistic optimization of interface and electrochemical properties of LNMO high-voltage cathode material via organic-inorganic double-layer coating[J]. Energy Storage Science and Technology, 2026, 15(9): 3462-3475.
刘婧珺, 王博同, 刘海龙, 等. 有机-无机双层包覆协同优化LiNi_0.5Mn_1.5O₄高压正极材料的界面及电化学性能[J]. 储能科学与技术, 2026, 15(9): 3462-3475. DOI: 10.19799/j.cnki.2095-4239.2026.0634. DOI：

LIU Jingjun, WANG Botong, LIU Hailong, et al. Synergistic optimization of interface and electrochemical properties of LNMO high-voltage cathode material via organic-inorganic double-layer coating[J]. Energy Storage Science and Technology, 2026, 15(9): 3462-3475. DOI： 10.19799/j.cnki.2095-4239.2026.0634.

摘要

为解决单一无机、单一聚合物包覆改性对尖晶石型LiNi

0.5

1.5

（LNMO）正极材料的改性局限，改善其高压工况下界面失效、过渡金属离子溶出及结构坍塌等缺陷，提升循环稳定性与倍率电化学性能，本工作提出一种有机-无机双层复合包覆改性策略。采用溶胶-凝胶法制备单晶LNMO基体，通过分步改性工艺构建LiNbO

无机导电层/PMMA-Li柔性聚合物层双层复合包覆体系，结合XRD、FTIR、SEM-EDS、TEM、ICP-MS金属离子溶出定量测试及系统性电化学测试，探究无机包覆负载量与有机聚合物添加量对LNMO微观结构、界面特性及电化学性能的调控规律，确定最优改性工艺。实验结果表明：质量分数为1.0% LiNbO

无机包覆层可有效保留LNMO完整晶型，构建高效锂离子传导通道，阻隔电解液与基体直接接触，对Mn、Ni过渡金属离子溶出的抑制效率超80%；在此基础上引入0.5% PMMA-Li柔性聚合物层，可有效缓冲循环应力，填补无机包覆层微观缺陷与循环微裂纹，规避颗粒表面开裂与结构剥离问题，实现无机层高离子电导与有机层高结构韧性的协同增效。改性样品LNMO-LN1.0-P5电化学性能优异，首圈库仑效率提升至91.36%，1 C倍率下200圈循环容量保持率达98.8%，5 C高倍率下100圈循环容量保持率为99.5%；55℃高温工况下100圈循环后容量保持率可达90.38%，200圈循环后电荷转移阻抗仅为5.1 Ω，固相锂离子扩散系数较原始LNMO提升两个数量级，离子传输动力学与倍率性能显著优化。本研究明晰了LiNbO

与PMMA-Li两相协同改性机理，有效解决了高压LNMO正极界面失效与结构劣化难题，为高压尖晶石镍锰酸锂正极材料的界面改性与高性能化发展提供了可行的工艺方案与实验参考。

Abstract

To address the modification limitations of a single inorganic or polymeric coating for spinel-type LiNi

0.5

1.5

(LNMO) cathode materials

mitigate interfacial failure

transition-metal dissolution and structural collapse under high-voltage conditions

and improve cycling stability and rate performance

this work proposes an organic-inorganic dual-layer composite coating modification strategy. Single-crystal LNMO su

bstrates are synthesized via the sol-gel method

and a dual-layer composite coating system consisting of a LiNbO

inorganic conductive layer and a PMMA-Li flexible polymeric layer is constructed through a stepwise modification process. XRD

FTIR

SEM-EDS

TEM

quantitative ICP-MS metal-dissolution measurements and comprehensive electrochemical tests are employed to investigate the modulating effects of inorganic coating loading and organic polymer dosage on the microstructure

interfacial properties and electrochemical performance of LNMO

and the optimal modification procedure is determined. The experimental results demonstrate that the 1.0% LiNbO

inorganic coating well preserves the crystal structure of LNMO

builds rapid Li

transport pathways

and isolates the substrate from direct electrolyte contact

achieving over 80% suppression efficiency for Mn and Ni transition-metal ion dissolution. On this basis

the introduction of a 0.5% PMMA-Li flexible polymeric layer effectively buffers cycling-induced stress

fills micro-defects and cycling-generated microcracks in the inorganic coating

and avoids particle surface cracking and structural delamination

thus realizing synergistic advantages of high ionic conductivity from the inorganic layer and superior structural toughness from the organic layer. The optimally modified sample LNMO-LN1.0-P5 exhibits outstanding electrochemical performance: its initial Coulombic efficiency reaches 91.36%; the capacity retention is 98.8% after 200 cycles at 1  C

and 99.5% after 100 cycles at a high rate of 5  C. At an elevated temperature of 55℃

the capacity retention attains 90.38% over 100 cycles. After 200 cycles

the charge-transfer resistance is only 5.1  Ω

and the solid-phase lithium-ion diffusion coefficient is enhanced by two orders of magnitude compared with pristine LNMO

indicating remarkably improved ion-transport kinetics and rate capability. This study clarifies the synergistic modification mechanism between LiNbO

and

PMMA-Li

and effectively alleviates interfacial failure and structural degradation of high-voltage LNMO cathodes. It provides a feasible technical route and experimental reference for interfacial modification and development of high-performance high-voltage spinel lithium nickel-manganese oxide cathode materials.

关键词

Keywords

references

HE M Y, LI R P, HAO M Z, et al. Novel design of eco-friendly high-performance thermoplastic elastomer based on polyurethane and ground tire rubber toward upcycling of waste tires[J]. Polymers, 2024, 16(17): 2448. DOI:10.3390/polym16172448.

HAO M Z, FENG D, REN D Y, et al. Bottom-up engineering strategies for electromagnetic shielding wood-based composites through Ca 2+ crosslink and graphene incorporation[J ] . Wood Material Science & Engineering, 2026, 21(1): 541-553. DOI:10. 1080/17480272.2024.2437507.

吕媛媛, 洪颖, 丁斌, 等. 新能源锂离子电池热失控性能研究[J]. 储能科学与技术, 2026, 15(2): 391-397.

LV Y Y, HONG Y, DING B, et al. Investigation on the thermal runaway performance of new energy lithium-ion cells[J]. Energy Storage Science and Technology, 2026, 15(2): 391-397.

李嘉鑫, 许铤, 肖秋平. 高镍三元锂离子电池热失控及产气特性研究[J]. 储能科学与技术, 2026, 15(4): 1387-1395.

LI J X, XU T, XIAO Q P. Research on thermal runaway and gas generation characteristics of high-nickel ternary lithium-ion cells[J]. Energy Storage Science and Technology, 2026, 15(4): 1387-1395.

DOSE W M, JOHNSON C S. Cathode pre-lithiation/sodiation for next-generation batteries[J]. Current Opinion in Electrochemistry, 2022, 31: 100827. DOI:10.1016/j.coelec.2021.100827.

郑立涵, 林俊楠, 陈平, 等. 基于集成学习和分位数回归的锂离子电池寿命预测方法[J]. 储能科学与技术, 2026, 15(6): 2380-2391.

ZHENG L H, LIN J N, CHEN P, et al. A framework fusing ensemble learning and quantile regression for lithium-ion battery life prediction[J]. Energy Storage Science and Technology, 2026, 15(6): 2380-2391.

TANG Z K, XUE Y F, TEOBALDI G, et al. The oxygen vacancy in Li-ion battery cathode materials[J]. Nanoscale Horizons, 2020, 5(11): 1453-1466. DOI:10.1039/d0nh00340a.

曾帅波, 李涌仪, 彭静, 等. 基于三元锂离子电池的导电剂优化设计[J]. 储能科学与技术, 2025, 14(3): 1187-1197.

ZENG S B, LI Y Y, PENG J, et al. Optimization design of conductive agent based on ternary lithium-ion battery[J]. Energy Storage Science and Technology, 2025, 14(3): 1187-1197.

梁文彪, 李世友, 崔孝玲, 等. 高电压LiNi 0.5 Mn 1.5 O 4 正极材料现状及展望[J ] . 硅酸盐通报, 2019, 38(11): 3450-3455.

LIANG W B, LI S Y, CUI X L, et al. Current status and prospect of high voltage LiNi 0.5 Mn 1.5 O 4 cathode materials[J ] . Bulletin of the Chinese Ceramic Society, 2019, 38(11): 3450-3455.

周兰, 李旺, 廖文俊. 界面化学对镍锰酸锂正极材料电化学性能影响的研究现状及分析[J]. 无机盐工业, 2021, 53(11): 17-24.

ZHOU L, LI W, LIAO W J. Research status and analysis of effect of interfacial chemistry on electrochemical properties of LiNi 0.5 Mn 1.5 O 4 cathode materials[J ] . Inorganic Chemicals Industry, 2021, 53(11): 17-24.

张明铝, 吴华城, 吴佳霓, 等. 高电压正极材料镍锰酸锂的改性研究进展[J]. 化工新型材料, 2024, 52(5): 1-4. DOI:10.19817/j.cnki.issn1006-3536.2024.07.045.

ZHANG M L, WU H C, WU J N, et al. Research progress on modification of high-voltage cathode material lithium nickel manganese oxide[J]. New Chemical Materials, 2024, 52(5): 1-4. DOI:10.19817/j.cnki.issn1006-3536.2024.07.045.

柳娜. 尖晶石LiNi 0.5 Mn 1.5 O 4 材料表面Li 3 PO 4 包覆改性与电化学性能[J ] . 硅酸盐学报, 2024, 52(6): 2032-2039.

LIU N. Surface modification and electrochemical performance of spinel LiNi 0.5 Mn 1.5 O 4 cathode material with Li 3 PO 4 coating[J ] . Journal of the Chinese Ceramic Society, 2024, 52(6): 2032-2039.

LIU J J, YUAN M L, LI Z, et al. Improving the electrochemical performance of single crystal LiNi 0.5 Mn 1.5 O 4 cathode materials by Y-Ti doping and unannealing process[J ] . Ceramics International, 2022, 48(24): 36490-36499. DOI:10.1016/j.ceramint.2022.08.209.

ZHAO J Z, LIU Y R, HE Y, et al. Li 4 Ti 5 O 12 epitaxial coating on LiNi 0.5 Mn 1.5 O 4 surface for improving the electrochemical performance through solvothermal-assisted processing[J ] . Journal of Alloys and Compounds, 2019, 779: 978-984. DOI:10.1016/j.jallcom.2018.11.152.

CHONG J, XUN S D, ZHANG J P, et al. Li 3 PO 4 -coated LiNi 0.5 Mn 1.5 O 4 : A stable high-voltage cathode material for lithium-ion batteries[J ] . Chemistry: A European Journal, 2014, 20(24): 7479-7485. DOI:10.1002/chem.201304744.

GAO C, LIU H P, BI S F, et al. Insight into the effect of graphene coating on cycling stability of LiNi 0.5 Mn 1.5 O 4 : Integration of structure-stability and s urface-stability[J ] . Journal of Materiomics, 2020, 6(4): 712-722. DOI:10.1016/j.jmat.2020.05.010.

LI S Y, LIANG W B, XIE J, et al. Synthesis of hollow microspheres LiNi 0.5 Mn 1.5 O 4 coated with Al 2 O 3 and characterization of the electrochemical capabilities[J ] . Journal of Electrochemical Energy Conversion and Storage, 2020, 17(3): 031007. DOI:10.1115/1.4045566.

BEN L B, YU H L, WU Y D, et al. Ta 2 O 5 coating as an HF barrier for improving the electrochemical cycling performance of high-voltage spinel LiNi 0.5 Mn 1.5 O 4 at elevated temperatures[J ] . ACS Applied Energy Materials, 2018: acsaem.8b01139. DOI:10.1021/acsaem.8b01139.

LIU Y, LU Z P, DENG C F, et al. A novel LiCoPO 4 -coated core-shell structure for spinel LiNi 0.5 Mn 1.5 O 4 as a high-performance cathode material for lithium-ion batteries[J ] . Journal of Materials Chemistry A, 2017, 5(3): 996-1004. DOI:10.1039/c6ta08659d.

LV S S, LI M Y, LUO X Y, et al. High-voltage LiNi 0.5 Mn 1.5 O 4 thin film cathodes stabilized by LiPON solid electrolyte coating to enhance cyclic stability and rate capability[J ] . Journal of Alloys and Compounds, 2020, 815: 151636. DOI:10.1016/j.jallcom. 2019.07.348.

CHEN A L, SHANG N, OUYANG Y, et al. Electroactive polymeric nanofibrous composite to drive in situ construction of lithiophilic SEI for stable lithium metal anodes[J ] . eScience, 2022, 2(2): 192-200. DOI:10.1016/j.esci.2022.02.003.

MAO J, DAI K H, XUAN M J, et al. Effect of chromium and niobium doping on the morphology and electrochemical performance of high-voltage spinel LiNi 0.5 Mn 1.5 O 4 cathode material[J ] . ACS Applied Materials & Interfaces, 2016, 8(14): 9116-9124. DOI:10.1021/acsami.6b00877.

SUN P, MA Y, ZHAI T Y, et al. High performance LiNi 0.5 Mn 1.5 O 4 cathode by Al-coating and Al 3+ -doping through a physical vapor deposition method[J ] . Electrochimica Acta, 2016, 191: 237-246. DOI:10.1016/j.electacta.2016.01.087.

ULU OKUDUR F, D'HAEN J, VRANKEN T, et al. Ti surface doping of LiNi 0.5 Mn 1.5 O 4- δ positive electrodes for lithium ion batteries[J ] . RSC Advances, 2018, 8(13): 7287-7300. DOI:10.1039/c7ra12932g.

KIM J H, HUQ A, CHI M F, et al. Integrated nano-domains of disordered and ordered spinel phases in LiNi 0.5 Mn 1.5 O 4 for Li-ion batteries[J ] . Chemistry of Materials, 2014, 26(15): 4377-4386. DOI:10.1021/cm501203r.

WANG J X, WANG N, NAN W Z, et al. Enhancement of electrochemical performance of LiCoO 2 cathode material at high cut-off voltage (4.5 V) by partial surface coating with graphene nanosheets[J ] . International Journal of Electrochemical Science, 2020, 15(9): 9282-9293. DOI:10.20964/2020.09.07.

KOYAMA Y, TANAKA I, ADACHI H, et al. First principles calculations of formation energies and electronic structures of defects in oxygen-deficient LiMn 2 O 4 [J ] . Journal of the Electrochemical Society, 2003, 150(1): A63. DOI:10.1149/1.1522720.

ZHENG J M, ZHU D R, YANG Y, et al. The effects of N -methyl- N -butylpyrrolidinium bis(trifluoromethylsulfonyl)imide-based electrolyte on the electrochemical performance of high capacity cathode material Li[Li 0.2 Mn 0.54 Ni 0.13 Co 0.13 ] O 2 [J ] . Electrochimica Acta, 2012, 59: 14-22. DOI:10.1016/j.electacta.2011.09.069.

GUO R, SHI P F, CHENG X Q, et al. Effect of ZnO modification on the performance of LiNi 0.5 Co 0.25 Mn 0.25 O 2 cathode material[J ] . Electrochimica Acta, 2009, 54(24): 5796-5803. DOI:10.1016/j.electacta.2009.05.034.

LIANG G M, PETERSON V K, SEE K W, et al. Developing high-voltage spinel LiNi 0.5 Mn 1.5 O 4 cathodes for high-energy-density lithium-ion batteries: Current achievements and future prospects[J ] . Journal of Materials Chemistry A, 2020, 8(31): 15373-15398. DOI:10.1039/d0ta02812f.

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