Engineering Fluorine-rich Double Protective Layer on Zn Anode for Highly Reversible Aqueous Zinc-ion Batteries.

The high thermodynamic instability and side reactions of Zn-metal anode (ZMA), especially at high current densities, greatly impede the commercialization of aqueous zinc-ion batteries (AZIBs). Herein, a fluorine-rich double protective layer strategy is proposed to obtain the high reversibility of AZIBs through the introduction of a versatile tetradecafluorononane-1,9-diol (TDFND) additive in aqueous electrolyte. TDFND molecule with large adsorption energy (-1.51 eV) preferentially absorbs on the Zn anode surface to form a Zn(OR)2 - (R=-CH2 -(CF2 )7 -CH2 -) cross-linking complex network, which balances space electric field and controls the Zn2+ ion flux, thus enabling the uniform and compact deposition of Zn (002) crystal planes. Meanwhile, TDFND with low Lowest unoccupied molecular orbital (LUMO, 0.10 eV) energy level is priorly decomposed to regulate the interfacial chemistry of ZMA by building a ZnF2 -rich solid electrode/electrolyte interface (SEI) layer. It is found that a 14 nm-thick SEI layer delivers excellent structural integrity to suppress parasitic reactions by blocking the direct contact of active water and ZMA. Consequently, the Zn electrode exhibits a superior cycling life over 430 h at 10 mA cm-2 and a high average Coulombic efficiency of 99.8 % at 5 mA cm-2 . Furthermore, a 68 mAh pouch cell delivers 80.3 % capacity retention for 1000 cycles.

Entanglement Added to Cross-Linked Chains Enables Tough Gelatin-Based Hydrogel for Zn Metal Batteries.

Currently, it is still challenging to develop a hydrogel electrolyte matrix that can successfully achieve a harmonious combination of mechanical strength, ionic conductivity, and interfacial adaptability. Herein, a multi-networked hydrogel electrolyte with a high entanglement effect based on gelatin/oxidized dextran/methacrylic anhydride, denoted as ODGelMA is constructed. Attribute to the Schiff base network formulation of ─RC═N─, oxidized dextran integrated gelatin chains induce a dense hydrophilic conformation group. Furthermore, addition of methacrylic anhydride through a grafting process, the entangled hydrogel achieves impressive mechanical features (6.8 MPa tensile strength) and high ionic conductivity (3.68 mS cm-1 at 20 °C). The ODGelMA electrolyte regulates the zinc electrode by circumventing dendrite growth, and showcases an adaptable framework reservoir to accelerate the Zn2+ desolvation process. Benefiting from the entanglement effect, the Zn anode achieves an outstanding average Coulombic efficiency (CE) of 99.8% over 500 cycles and cycling stability of 900 h at 5 mA cm-2 and 2.5 mAh cm-2. The Zn||I2 full cell yields an ultra-long cycling stability of 10 000 cycles with a capacity retention of 92.4% at 5 C. Furthermore, a 60 mAh single-layer pouch cell maintains a stable work of 350 cycles.