Tris(trimethylsilyl)borate (TMSB) has been intensively studied to improve the performances of lithium-ion batteries. However, it is still an interesting issue needed to be resolved for the research on the Li⁺ solvation structure affected by TMSB additive. Herein, the electrochemical tests, quantum chemistry calculations, potential-resolved in-situ electrochemical impedance spectroscopy measurements and surface analyses were used to explore the effects of Li⁺ solvation structure with TMSB additive on the formation of the cathode electrolyte interface (CEI) film in LiNi_0.8Co_0.1Mn_0.1O₂/Li half cells. The results reveal that the TMSB additive is easy to complex with Li⁺ ion, thus weaken the intermolecular force between Li⁺ ions and ethylene carbonate solvent, which is benefit for the cycle performance. Besides, the changed Li⁺ solvation structure results in a thin and dense CEI film containing compounds with Si–O and B–O bonds which is favorable to the transfer of Li⁺ ions. As a result, the performances of the LNCM811/Li half cells are effectively improved. This research provides a new idea to construct a high-performance CEI film by adjusting the Li⁺ solvation structures.

三（三甲基甲硅烷基）硼酸酯（TMSB）已被深入研究以提高锂离子电池的性能。然而，研究受TMSB添加剂影响的Li ⁺溶剂化结构仍然是一个需要解决的有趣问题。在此，电化学测试、量子化学计算、电位分辨原位电化学阻抗谱测量和表面分析被用来探索含有 TMSB 添加剂的 Li ⁺溶剂化结构对阴极电解质界面（CEI）膜形成的影响。 LiNi _0.8 Co _0.1 Mn _0.1 O ₂ /Li 半电池。结果表明，TMSB添加剂容易与Li ⁺离子，从而减弱 Li ⁺离子与碳酸亚乙酯溶剂之间的分子间作用力，有利于循环性能。此外，改变的 Li ⁺溶剂化结构导致薄而致密的 CEI 膜包含具有 Si-O 和 B-O 键的化合物，这有利于 Li ⁺离子的转移。因此，LNCM811/Li 半电池的性能得到有效提升。该研究为通过调整Li ⁺溶剂化结构构建高性能CEI薄膜提供了新思路。