Molecular Engineering Enables Hydrogel Electrolyte with Ionic Hopping Migration and Self-Healability toward Dendrite-Free Zinc-Metal Anodes

Kaiping Zhu; Jie Luo; Dehe Zhang; Nanyang Wang; Shibo Pan; Shujin Zhou; Zhenjie Zhang; Gengde Guo; Peng Yang; Yuan Fan; Shisheng Hou; Zhipeng Shao; Shizhuo Liu; Lin Lin; Pan Xue; Guo Hong; Yurong Yang; Yagang Yao

doi:10.1002/adma.202311082

Molecular Engineering Enables Hydrogel Electrolyte with Ionic Hopping Migration and Self-Healability toward Dendrite-Free Zinc-Metal Anodes

Adv Mater. 2024 May;36(19):e2311082. doi: 10.1002/adma.202311082. Epub 2024 Feb 16.

Authors

Kaiping Zhu¹, Jie Luo², Dehe Zhang¹, Nanyang Wang¹, Shibo Pan³, Shujin Zhou⁴, Zhenjie Zhang⁵, Gengde Guo¹, Peng Yang¹, Yuan Fan², Shisheng Hou², Zhipeng Shao¹, Shizhuo Liu¹, Lin Lin¹, Pan Xue⁶, Guo Hong⁷, Yurong Yang¹, Yagang Yao¹

Affiliations

¹ 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.
² Key Laboratory of Multifunctional Nanomaterials and Smart Systems, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, China.
³ Faculty of Physics, Central South University, Changsha, 410083, P. R. China.
⁴ Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
⁵ Center of Energy Storage Materials & Technology, College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210023, China.
⁶ School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, China.
⁷ Department of Materials Science and Engineering & Center of Super-Diamond and Advanced Films, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, SAR 999077, China.

PMID: 38288858
DOI: 10.1002/adma.202311082

Abstract

Hydrogel electrolytes (HEs), characterized by intrinsic safety, mechanical stability, and biocompatibility, can promote the development of flexible aqueous zinc-ion batteries (FAZIBs). However, current FAZIB technology is severely restricted by the uncontrollable dendrite growth arising from undesirable reactions between the HEs with sluggish ionic conductivity and Zn metal. To overcome this challenge, this work proposes a molecular engineering strategy, which involves the introduction of oxygen-rich poly(urea-urethane) (OR-PUU) into polyacrylamide (PAM)-based HEs. The OR-PUU/PAM HEs facilitate rapid ion transfer through their ionic hopping migration mechanism, resulting in uniform and orderly Zn²⁺ deposition. The abundant polar groups on the OR-PUU molecules in OR-PUU/PAM HEs break the inherent H-bond network, tune the solvation structure of hydrated Zn²⁺, and inhibit the occurrence of side reactions. Moreover, the interaction of hierarchical H-bonds in the OR-PUU/PAM HEs endows them with self-healability, enabling in situ repair of cracks induced by plating/stripping. Consequently, Zn symmetric cells incorporating the novel OR-PUU/PAM HEs exhibit a long cycling life of 2000 h. The resulting Zn-MnO₂ battery displays a low capacity decay rate of 0.009% over 2000 cycles at 2000 mA g^-1. Overall, this work provides valuable insights to facilitate the realization of dendrite-free Zn-metal anodes through the molecular engineering of HEs.

Keywords: dendrite‐free Zn‐metal anode; hydrogel electrolytes; ionic hopping migration; molecular engineering; self‐healability.

Abstract

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