Stabilizing Interface pH by Mixing Electrolytes for High-Performance Aqueous Zn Metal Batteries.

Aqueous zinc metal batteries with mild acidic electrolytes are considered promising candidates for large-scale energy storage. However, the Zn anode suffers from severe Zn dendrite growth and side reactions due to the unstable interfacial pH and the absence of a solid electrolyte interphase (SEI) protective layer. Herein, a novel and simple mixed electrolyte strategy is proposed to address these problems. The mixed electrolytes of 2 M ZnSO4 and 2 M Zn (CF3 SO3 )2 can efficiently buffer the interfacial pH and induce the in situ formation of the organic-inorganic SEI layer, which eliminates dendrite growth and prevents side reactions. As a result, Zn anodes in mixed electrolyte exhibit a lifespan enhancement over 400 times, endure stable cycling over 270 h at a high DOD of 62% and achieve high Zn plating/stripping reversibility with an average CE of 99.5% for 1000 cycles at 1 mA cm-2 . The findings pave the way for developing practical electrolyte systems for Zn batteries.

Stabilizing Interface pH by N-Modified Graphdiyne for Dendrite-Free and High-Rate Aqueous Zn-Ion Batteries.

Zn dendrite issue was intensively studied via tuning zinc ion flux. pH change seriously influences dendrite formation, while its importance has not been revealed. Here, we construct a N-modification graphdiyne interface (NGI) to stabilize pH by mediating hydrated zinc ion desolvation. Operando pH detection reveals pH stabilization by NGI. This works with pores in NGI to achieve dendrite-free Zn deposition and an increased symmetric cell lifespan by 116 times. Experimental and theoretical results owe pH stabilization to desolvation with a reduced activation energy achieved by electron transfer from solvation sheath to N atom. The efficient desolvation ensures that electron directly transfers from substrate to Zn2+ (rather than the coordinated H2 O), avoiding O-H bond splitting. Hence, Zn-V6 O13 battery achieves a long lifespan at 20.65 mA cm-2 and 1.07 mAh cm-2 . This work reveals the significance of interface pH and provides a new approach to address Zn dendrite issue.

High-Rate, Large Capacity, and Long Life Dendrite-Free Zn Metal Anode Enabled by Trifunctional Electrolyte Additive with a Wide Temperature Range.

Aqueous Zn-ion batteries (AZIBs) have been recognized as promising energy storage devices due to their high theoretical energy density and cost-effectiveness. However, side reactions and Zn dendrite generation during cycling limit their practical application. Herein, ammonium acetate (CH3 COONH4 ) is selected as a trifunctional electrolyte additive to enhance the electrochemical performance of AZIBs. Research findings show that NH4 + (oxygen ligand) and CH3 COO- (hydrogenligand) with preferential adsorption on the Zn electrode surface can not only hinder Zn anode directly contact with active H2 O, but also regulate the pH value of the electrolyte, thus suppressing the parasitic reactions. Additionally, the formed SEI is mainly consisted of Zn5 (CO3 )2 (OH)6 with a high Zn2+ transference number, which could achieve a dendrite-free Zn anode by homogenizing Zn deposition. Consequently, the Zn||Zn symmetric batteries with CH3 COONH4 -based electrolyte can operate steadily at an ultrahigh current density of 40 mA cm-2 with a cumulative capacity of 6880 mAh cm-2 , especially stable cycling at -10 °C. The assembled Zn||MnO2 full cell and Zn||activated carbon capacitor also deliver prominent electrochemical reversibility. This work provides unique understanding of designing multi-functional electrolyte additive and promotes a long lifespan at ultrahigh current density for AZIBs.