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Volume 117
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Orbital-hybridization-driven electron transfer triggers the reductive susceptibility of solvated cyclic carbonates
Tong Wu a, Chen-Chen Wang a, Jin-Hao Zhang a, Wen-Ping Ju a, Zhong-Yang Liu a, Xi Xu a, Jin-Hao Meng c, Yu-Zhen Zhao b *, Long Kong a *
a School of Flexible Electronics, Northwestern Polytechnical University, Xi'an, 710129, China
b Shaanxi Key Laboratory of Liquid Crystal Polymer Intelligent Display, Technological Institute of Materials & Energy Science (TIMES), School of Materials and New Energy, Xijing University, Xi'an, 710123, China
c School of Electrical Engineering, Xi'an Jiaotong University, Xi'an, 710049, China
10.1016/j.partic.2026.08.018
Volume 117, October 2026, Pages 550-557
Received 8 August 2026, Revised 16 August 2026, Accepted 18 August 2026, Available online 19 August 2026, Version of Record 28 August 2026.
E-mail: zhaoyuzhen@xijing.edu.cn; iamlkong@nwpu.edu.cn
Highlights

• Analyzing factors governing solvent decomposition via intrinsic physicochemical properties.

• Analyzing factors influencing decomposition based on Li+–solvent interactions.

• Elucidating solvent decomposition factors via Li+–solvent interactions.

• Revealing reductive decomposition mechanisms via molecular orbital analysis.


Abstract

Carbonate-based solvents are widely used in lithium-ion batteries due to their excellent solvation ability, high fluidity after blending, and the capability to form a solid electrolyte interphase (SEI) film through sacrificial reductive decomposition. However, as the core components of the electrolyte, the decomposition mechanism and microscopic influencing factors of cyclic carbonates remain unclear. To address this issue, this study employs multiple methods to comparatively investigate the properties and reduction behaviour of several cyclic carbonates. The results show that cyclic carbonates are more prone to reductive decomposition after forming solvation structures with lithium ions. Furthermore, influenced by molecular structure, the enhancement magnitude of the decomposition ability after solvation exhibits significant differences among different solvents. By analyzing the electronic structures and frontier orbitals, this paper reveals the microscopic mechanism: the leap in reduction ability in the solvated state essentially originates from the orbital hybridization effect between solvent molecules and the central lithium ion. This work clarifies how cyclic carbonates decompose via electron transfer, offering key theoretical insights to guide electrolyte optimization and electrode interface modification.

Graphical abstract
Keywords
Cyclic carbonates; Reductive decomposition; Orbital hybridization; Steric effects; Electronic effects
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