Lithium-ion intercalation by coupled ion-electron transfer

27 May 2024, Version 2


Lithium-ion batteries are powering a revolution in electrification, but the underlying intercalation mechanism at the electrified interface remains poorly understood. Here, we provide experimental and theoretical evidence that lithium intercalation occurs by coupled ion-electron transfer (CIET), in which classical ion transfer from the electrolyte is coupled with quantum-mechanical electron transfer from the electrode to form an ion-electron pair in the reduced state. Current-voltage responses and reaction-limited capacities, corresponding to small and large overpotentials, respectively, were measured for common electrode materials and linked by the theory. The experiments showed universal dependence of the (de-)intercalation rate on Li-ion filling fraction, as well as temperature and electrolyte effects consistent with the theory. These results could be used to guide the design of high-rate battery interfaces that maximize the CIET reaction-limited current.


Ion intercalation
Coupled ion-electron transfer
Li-ion batteries
Reaction-limited rate capability
Experiments and theories

Supplementary materials

Supplementary Materials for "Lithium-ion intercalation by coupled ion-electron transfer"
Materials and Methods Supplementary Text Figs. S1 to S35 Tables S1 to S6


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