原位交联的聚合物包覆层稳定LiNi0.6Co0.2Mn0.2O2正极

刘婧超; 薛金鑫; 刘骁; 张子涵; 周建军; 李林

doi:10.11777/j.issn1000-3304.2026.26132

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原位交联的聚合物包覆层稳定LiNi_0.6Co_0.2Mn_0.2O₂正极

研究论文 | 更新时间：2026-07-23

- 原位交联的聚合物包覆层稳定LiNi_0.6Co_0.2Mn_0.2O₂正极
- Stabilizing LiNi_0.6Co_0.2Mn_0.2O₂Cathode via In situ Cross-linked Polymer Coating
- 高分子学报 2026年页码：1-13
- 作者机构：
  
  1.北京师范大学化学学院北京 100875
  2.中国电子信息产业发展研究院集成电路研究所北京 100846
- 作者简介：
  
  E-mail: pla_zjj@bnu.edu.cn
  E-mail: lilinll@bnu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 22475021)
- DOI：10.11777/j.issn1000-3304.2026.26132
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7659
- 收稿：2026-04-22，
  
  录用：2026-06-09，
  
  网络首发：2026-07-23，
- 稿件说明：
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刘婧超, 薛金鑫, 刘骁, 张子涵, 周建军, 李林. 原位交联的聚合物包覆层稳定LiNi_0.6Co_0.2Mn_0.2O₂正极. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26132. CSTR: 32057.14.GFZXB.2026.7659.

Liu, J. C.; Xue, J. X.; Liu, X.; Zhang, Z. H.; Zhou, J. J.; Li, L. Stabilizing LiNi_0.6Co_0.2Mn_0.2O₂ cathode via in situ cross-linked polymer coating. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26132. CSTR: 32057.14.GFZXB.2026.7659.
刘婧超, 薛金鑫, 刘骁, 张子涵, 周建军, 李林. 原位交联的聚合物包覆层稳定LiNi_0.6Co_0.2Mn_0.2O₂正极. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26132. CSTR: 32057.14.GFZXB.2026.7659. DOI：

Liu, J. C.; Xue, J. X.; Liu, X.; Zhang, Z. H.; Zhou, J. J.; Li, L. Stabilizing LiNi_0.6Co_0.2Mn_0.2O₂ cathode via in situ cross-linked polymer coating. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26132. CSTR: 32057.14.GFZXB.2026.7659. DOI：

摘要

高电压层状锂镍钴锰氧化物正极材料的界面不稳定，存在电解液过度分解、过渡金属溶出和阳离子混排等问题，严重制约其循环寿命. 本研究设计并合成了一种同时含羟基和氰基的丙烯酸酯类共聚物(PMHC)，在正极材料浆料制备过程中包覆在LiNi

0.6

0.2

(NCM

622)颗粒表面，并利用Ritter反应使聚合物包覆层原位交联，形成包覆层稳定的正极(PMHC@NCM)来提升电池的性能. 密度泛函理论计算发现氰基与NCM622 (-1 0 0)晶面的结合能(-24.35 eV)远高于PVDF的含氟基团(-14.62 eV)，有利于聚合物的优先吸附包覆. 傅里叶变换红外光谱和X射线光电子能谱(XPS)研究表明PMHC聚合物在Lewis酸存在时发生了交联. 透射电镜证实了交联PMHC聚合物在NCM622表面的包覆. 循环伏安测试证明包覆层显著降低了极化，提高Li

的表观扩散系数. 电池测试结果显示，包覆有益于维持正极材料循环过程中结构的稳定性，采用PMHC@NCM正极的电池在0.5 C循环400圈后仍能维持非常高的放电比容量(146.7 mAh·g

-1

)和库仑效率(99.78%). XPS分析进一步揭示，包覆的交联聚合物参与了正极界面层的形成，而且这种交联聚合物衍生的界面层有效抑制了阳离子混排、过渡金属溶出和电解液分解. 本研究展示了一种利用聚合物包覆后利用Ritter反应原位交联来稳定高压正极材料界面的新策略，为改善和提高高能量密度锂离子电池的循环性能提供了新的思路.

Abstract

The interfacial instability of high-voltage layered lithium nickel-cobalt-manganese oxide cathode materials

characterized by excessive electrolyte decomposition

transition metal dissolution

and cation mixing

severely limits their cycle life. In this work

an acrylate copolymer (PMHC) containing both hydroxyl and cyano groups was designed and synthesized. This copolymer coated the surface of LiNi

0.6

0.2

(NCM622) particles during the cathode slurry preparation process and undergoes

in situ

cross-linking

via

the Ritter reaction

forming

a stable polymer interface layer to enhance cathode performance. Density functional theory (DFT) calculations revealed that the binding energy between the cyano group and the NCM622 (-1 0 0) crystal plane (-24.35 eV) was much higher than that of the fluorine-containing group in PVDF (-14.62 eV)

facilitating preferential adsorption and coating of the polymer. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) studies indicated that PMHC polymer undergoes cross-linking in the presence of Lewis acid. Transmission electron microscopy (TEM) confirmed the successful coating of the cross-linked PMHC polymer on the NCM622 surface. Cyclic voltammetry (CV) tests demonstrated that the coating layer significantly reduced polarization and increased the apparent diffusion coefficient of Li

. Battery test results showed that the coating layer contributed to the structure stability of the cathode material. The PMHC@NCM cell exhibited a very high specific discharge capacity (146.7 mAh·g

-1

) and Coulombic efficiency (99.78%) after 400 cycles at 0.5 C. XPS analysis further revealed that the cross-linked polymer coating participates in the formation of the cathode electrolyte interface (CEI) layer

and this polymer-derived CEI effectively suppressed cation mixing

transition metal dissolution

and electrolyte decomposition. This work presents a new strategy for stabilizing high-voltage cathode material interfaces through polymer coating followed by

in situ

cross-linking

offering a novel approach to improve the cycle life of high energy-density lithium-ion batteries.

关键词

Keywords

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