Rational Design of a Bilayer Interface for Long‐Term Stability of Zn Anodes and MnO<sub>2</sub> Cathodes

K Kaiping Zhu (National Laboratory of Solid State Microstructures College of Engineering and Applied Sciences Jiangsu Key Laboratory of Artificial Functional Materials Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210093 China) W Wubin Zhuang (National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210093 China) N Nanyang Wang (NTI‐NTU Corporate Laboratory Nanyang Technological University Singapore 637662 Singapore) K Kai Zhang L Lin Lin Z Zhipeng Shao C Chaowei Li W Wenhui Wang (Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, Frontiers Center for Materiobiology and Dynamic Chemistry) S Shizhuo Liu (National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210093 China) P Peng Yang P Pan Xue Q Qichong Zhang (Key Laboratory of Multifunctional Nanomaterials and Smart Systems, Suzhou Institute of Nano-Tech and Nano-Bionics) G Guo Hong Y Yagang Yao (National Laboratory of Solid State Microstructures College of Engineering and Applied Sciences Jiangsu Key Laboratory of Artificial Functional Materials Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210023 P.R. China)

Abstract

AbstractUnderstanding the composition–characteristics–performance relationship of the electrolyte–electric double layer–electrode–electrolyte interface (EEI) is crucial to construct stable EEIs for high‐performance aqueous Zn–MnO2 batteries (AZMBs). However, the interaction mechanisms in AZMBs remain unclear. This work introduces sodium thioctate (ST) into ZnSO4 electrolyte to construct a stable bilayer EEI on both Zn and MnO2 electrodes. First, zincophilic ST regulates the solvation structure of hydrated Zn2+, suppressing corrosion and the hydrogen evolution reaction. Second, the specific adsorption of ST reconstructs the inner Helmholtz plane, facilitating the desolvation of hydrated Zn2+ and homogenizing charge distribution. Finally, ST molecules undergo reversible polymerization at the interface, forming a stable bilayer EEI with a poly(zinc thioctate) outer layer and a ZnS–organic amorphous inner layer, which ensures uniform zinc‐ion flux and enhances mechanical stability. Additionally, the dynamic disulfide bonds in ST further enable self‐regulation and self‐healing of the interface, mitigating damage during cycling. As a result, the ST‐enhanced Zn symmetric battery achieves 7800 cycles at 60 mA cm−2, while the AZMB exhibits only 0.0014% capacity decay over 10 000 cycles at 2000 mA g−1. This bilayer EEI engineering strategy offers effective guidance for the rational design of safe and long‐life aqueous zinc‐ion batteries.

Article Details

Volume / Issue Vol. 37, Issue 24
Published June 01, 2025
ISSN 0935-9648
Publisher Unknown Publisher

Journal Info

Advanced Materials

Unknown Publisher

ISSN: 0935-9648 Physical Sciences

Authors (14)

K

Kaiping Zhu

National Laboratory of Solid State Microstructures College of Engineering and Applied Sciences Jiangsu Key Laboratory of Artificial Functional Materials Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210093 China

W

Wubin Zhuang

National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210093 China

N

Nanyang Wang

NTI‐NTU Corporate Laboratory Nanyang Technological University Singapore 637662 Singapore

K

Kai Zhang

L

Lin Lin

Z

Zhipeng Shao

C

Chaowei Li

W

Wenhui Wang

Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, Frontiers Center for Materiobiology and Dynamic Chemistry

S

Shizhuo Liu

National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210093 China

P

Peng Yang

P

Pan Xue

Q

Qichong Zhang

Key Laboratory of Multifunctional Nanomaterials and Smart Systems, Suzhou Institute of Nano-Tech and Nano-Bionics

G

Guo Hong

Y

Yagang Yao

National Laboratory of Solid State Microstructures College of Engineering and Applied Sciences Jiangsu Key Laboratory of Artificial Functional Materials Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210023 P.R. China