Quasi-Solid Electrolyte Interphase Boosting Charge and Mass Transfer for Dendrite-Free Zinc Battery

Abstract

The practical applications of zinc metal batteries are plagued by the dendritic propagation of its metal anodes due to the limited transfer rate of charge and mass at the electrode/electrolyte interphase. To enhance the reversibility of Zn metal, a quasi-solid interphase composed by defective metal–organic framework (MOF) nanoparticles (D-UiO-66) and two kinds of zinc salts electrolytes is fabricated on the Zn surface served as a zinc ions reservoir. Particularly, anions in the aqueous electrolytes could be spontaneously anchored onto the Lewis acidic sites in defective MOF channels. With the synergistic effect between the MOF channels and the anchored anions, Zn2+ transport is prompted significantly. Simultaneously, such quasi-solid interphase boost charge and mass transfer of Zn2+, leading to a high zinc transference number, good ionic conductivity, and high Zn2+ concentration near the anode, which mitigates Zn dendrite growth obviously. Encouragingly, unprecedented average coulombic efficiency of 99.8% is achieved in the Zn||Cu cell with the proposed quasi-solid interphase. The cycling performance of D-UiO-66@Zn||MnO2 (~ 92.9% capacity retention after 2000 cycles) and D-UiO-66@Zn||NH4V4O10 (~ 84.0% capacity retention after 800 cycles) prove the feasibility of the quasi-solid interphase.

Porous framework materials for stable Zn anodes in aqueous zinc-ion batteries

“…This improvement occurs due to the fixation of anions to the electropositive oxygen vacancies through Lewis acid–base reactions. Based on this idea, Xu et al 66 designed a defect-rich MOF (D-UiO-66) as a quasi-solid electrode/electrolyte interlayer on the Zn anode, which is filled with two types of Zn salt electrolytes as a Zn 2+ reservoir. Additionally, the MOF channels were modified with anionic functional groups (such as –SO 3 − ), which can enhance cation diffusion within the pores.…”

Advances in functional organic material-based interfacial engineering on metal anodes for rechargeable secondary batteries

“…The well-dispersed multifunctional polymers could be expected to obtain a hydrogen bond network with flexible matrix for efficient Zn ion transport and interface contact. 198 For example, polyzwitterionic hydrogel electrolytes are promising platforms to design safe, economic, and stable quasi-solid-state zinc metal batteries. The charged groups of the zwitterionic polymer not only homogenized the Zn 2+ distribution, but also improved the ionic conductivity of an SPE to 32.0 mS cm −1 at room temperature.…”

Study of a novel supramolecular hydrogel electrolyte for aqueous zinc ion batteries

“…29,30 Due to the unique three-dimensional network structure of hydrogels, hydrogel electrolytes combine the merits of liquid and solid electrolytes. 31,32 Hydrogel electrolytes not only possess high conductivity but also can effectively prevent the dissolution of active materials and the leakage of liquid. 33,34 In addition, hydrogel electrolytes have been verified to be effective in suppressing the Zn dendrites and hazardous side reactions, attributed to the interactions between Zn 2+ and the functional groups in hydrogels.…”