Bismuth chloride additive regulated anode interphase and kinetics in manganese-ion batteries

Abstract

The use of nonaqueous electrolyte in manganese-ion batteries (MIBs) has attracted increasing scientific attention because of their unique properties. These systems significantly reduce water-molecule interference in electrode reactions, effectively precluding unwanted side reactions such as the hydrogen evolution reaction, which commonly occurs in aqueous electrolytes. Nonaqueous electrolyte development is still a challenge, though. Mn²⁺ has a high charge density, which leads to sluggish Mn²⁺ kinetics and greatly limits the development of nonaqueous MIBs. In this study, BiCl₃ is used as an electrolyte additive to enhance the reaction kinetics of Mn²⁺ in a diglyme-based nonaqueous electrolyte. Electrochemical testing shows that the polarization voltage of Mn||Mn symmetric cells is greatly reduced following the addition of BiCl₃. Full characterization by X-ray diffraction and scanning electron microscopy, combined with density functional theory calculations, suggests that Bi³⁺ undergoes a spontaneous galvanic replacement reaction with the Mn anode. This process enables the in situ formation of a Bi-containing interphase, which helps reduce the activation barrier for charge transfer. Thus, the full cell with a Cu_1.8S cathode delivered an improved average discharge capacity of 166.1 mAh g^-1 over 200 cycles at 100 mA g^-1. This work provides perspectives for designing the interfacial chemistry of MIBs.

Keywords

Nonaqueous manganese-ion battery / electrolyte additive / interface modification / electrochemical reaction kinetics

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