Simultaneous Manipulation of Electric Double Layer and Zn (100) Deposition Enabled by Anions for Highly Stable Zn Anodes

S Si Tang (State Key Laboratory of Tropic Ocean Engineering Materials and Materials Evaluation Hainan Provincial Key Lab of Fine Chem Hainan University Haikou China) Q Qingyi Wei B Baoquan Liu (Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,) J Jinlin Yang (Department of Chemistry, National University of Singapore, 12 Science Drive 2, Singapore 117549, Singapore) H Haizhen Jiang (State Key Laboratory of Tropic Ocean Engineering Materials and Materials Evaluation Hainan Provincial Key Lab of Fine Chem Hainan University Haikou China) Y Yanzeng Ge D Daoxiong Wu J Jing Li T Tianyu Qiu H Hui Zhang (The Fourth Hospital of Hebei Medical University Shijiazhuang China) X Xinlong Tian (School of Marine Technology and Equipment, State Key Laboratory of Tropic Ocean Engineering Materials and Materials Evaluation, School of Chemistry and Chemical Engineering)

Abstract

Abstract Controlling the growth orientation of zinc (Zn) is an effective method of stabilizing Zn anodes. Although Zn (100) exhibits faster Zn electroplating/stripping kinetics than Zn (002), its high chemical reactivity results in susceptibility to water‐induced side reactions. Herein, a two‐pronged electrolyte engineering strategy is proposed to enhance the reversibility of Zn anodes, that is, modulating vertically oriented Zn (100) plating while simultaneously constructing a water‐poor electrical double layer (EDL). Mechanistic studies revealed that the difluoro(oxalato)borate (DFOB − ) anions of sodium‐difluoro(oxalato)borate (NaDFOB) function as a Zn 2+ trapping agent at the inner Helmholtz layer, displacing active water molecules and inducing the preferential deposition of Zn on the Zn (100) crystal facets, thus effectively inhibiting both side reactions and dendrite growth. Consequently, a symmetrical cell with the ZnSO 4 /NaDFOB electrolyte exhibited a long lifetime of over 950 h under severe conditions of 10 mA cm −2 and 5 mAh cm −2 . Furthermore, a practical Zn||NH 4 V 4 O 10 pouch cell could achieves a high capacity of 156 mAh at industrial‐level mass loading of 16.6 mg cm −2 . This work provides insights for achieving stable Zn anodes via electrolyte engineering‐triggered crystallographic orientation and EDL regulation.

Article Details

Volume / Issue Vol. 64, Issue 36
Published September 01, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (11)

S

Si Tang

State Key Laboratory of Tropic Ocean Engineering Materials and Materials Evaluation Hainan Provincial Key Lab of Fine Chem Hainan University Haikou China

Q

Qingyi Wei

B

Baoquan Liu

Petroleum and Chemical Industry Key Laboratory of Organic Electrochemical Synthesis, State Key Laboratory of Green Chemical Synthesis and Conversion, College of Chemical Engineering, Zhejiang University of Technology,

J

Jinlin Yang

Department of Chemistry, National University of Singapore, 12 Science Drive 2, Singapore 117549, Singapore

H

Haizhen Jiang

State Key Laboratory of Tropic Ocean Engineering Materials and Materials Evaluation Hainan Provincial Key Lab of Fine Chem Hainan University Haikou China

Y

Yanzeng Ge

D

Daoxiong Wu

J

Jing Li

T

Tianyu Qiu

H

Hui Zhang

The Fourth Hospital of Hebei Medical University Shijiazhuang China

X

Xinlong Tian

School of Marine Technology and Equipment, State Key Laboratory of Tropic Ocean Engineering Materials and Materials Evaluation, School of Chemistry and Chemical Engineering