Shifting redox reaction equilibria on demand using an orthogonal redox cofactor

Aspacio, Derek; Zhang, Yulai; Cui, Youtian; Luu, Emma; King, Edward; Black, William B; Perea, Sean; Zhu, Qiang; Wu, Yongxian; Luo, Ray; Siegel, Justin B; Li, Han

doi:10.1038/s41589-024-01702-5

Chemical redox reactions between redox shuttles and lithium-ion battery particles have applications in electrochemical systems including redox-mediated flow batteries, photo-assisted lithium-ion batteries, and lithium-ion battery overcharge protection. These previous studies, combined with interest in chemical redox of battery materials in general, has resulted in previous reports of the chemical oxidation and/or reduction of solid lithium-ion materials. However, in many of these reports, a single redox shuttle is the focus and/or the experimental conditions are relatively limited. Herein, a study of chemical redox for a series of redox shuttles reacted with a lithium-ion battery cathode material will be reported. Both oxidation and reduction of the solid material with redox shuttles as a function of time will be probed using ferrocene derivatives with different half-wave potentials. The progression of the chemical redox was tracked by using electrochemical analysis of the redox shuttles in a custom electrochemical cell, and rate constants for chemical redox were extracted from using two different models. This study provides evidence that redox shuttle-particle interactions play a role in the overall reaction rate, and more broadly support that this experimental method dependent on electrochemical analysis can be applied for comparison of redox shuttles reacting with solid electroactive materials.

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