Self-assembled hydrated copper coordination compounds as ionic conductors for room temperature solid-state batteries

Xiao Zhan; Miao Li; Xiaolin Zhao; Yaning Wang; Sha Li; Weiwei Wang; Jiande Lin; Zi-Ang Nan; Jiawei Yan; Zhefei Sun; Haodong Liu; Fei Wang; Jiayu Wan; Jianjun Liu; Qiaobao Zhang; Li Zhang

doi:10.1038/s41467-024-45372-2

Self-assembled hydrated copper coordination compounds as ionic conductors for room temperature solid-state batteries

Nat Commun. 2024 Feb 5;15(1):1056. doi: 10.1038/s41467-024-45372-2.

Authors

Xiao Zhan¹, Miao Li¹, Xiaolin Zhao², Yaning Wang², Sha Li¹, Weiwei Wang¹, Jiande Lin¹, Zi-Ang Nan¹, Jiawei Yan¹, Zhefei Sun¹, Haodong Liu³, Fei Wang⁴, Jiayu Wan⁵, Jianjun Liu⁶, Qiaobao Zhang^{7

8}, Li Zhang⁹

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, College of Materials, Tan Kah Kee Innovation Laboratory, Collaborative Innovation Center of Chemistry for Energy Materials, Xiamen University, Xiamen, 361005, Fujian, China.
² State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China.
³ Chemical Engineering, UC San Diego, La Jolla, CA, 92093, USA.
⁴ Department of Materials Science, Fudan University, Shanghai, 200433, China.
⁵ Future Battery Research Center, Global Institute of Future Technology, Shanghai Jiaotong University, Shanghai, 200240, China.
⁶ State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China. jliu@mail.sic.ac.cn.
⁷ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, College of Materials, Tan Kah Kee Innovation Laboratory, Collaborative Innovation Center of Chemistry for Energy Materials, Xiamen University, Xiamen, 361005, Fujian, China. zhangqiaobao@xmu.edu.cn.
⁸ Shenzhen Research Institute of Xiamen University, Shenzhen, 518000, China. zhangqiaobao@xmu.edu.cn.
⁹ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, College of Materials, Tan Kah Kee Innovation Laboratory, Collaborative Innovation Center of Chemistry for Energy Materials, Xiamen University, Xiamen, 361005, Fujian, China. zhangli81@xmu.edu.cn.

Abstract

As the core component of solid-state batteries, neither current inorganic solid-state electrolytes nor solid polymer electrolytes can simultaneously possess satisfactory ionic conductivity, electrode compatibility and processability. By incorporating efficient Li⁺ diffusion channels found in inorganic solid-state electrolytes and polar functional groups present in solid polymer electrolytes, it is conceivable to design inorganic-organic hybrid solid-state electrolytes to achieve true fusion and synergy in performance. Herein, we demonstrate that traditional metal coordination compounds can serve as exceptional Li⁺ ion conductors at room temperature through rational structural design. Specifically, we synthesize copper maleate hydrate nanoflakes via bottom-up self-assembly featuring highly-ordered 1D channels that are interconnected by Cu²⁺/Cu⁺ nodes and maleic acid ligands, alongside rich COO^- groups and structural water within the channels. Benefiting from the combination of ion-hopping and coupling-dissociation mechanisms, Li⁺ ions can preferably transport through these channels rapidly. Thus, the Li⁺-implanted copper maleate hydrate solid-state electrolytes shows remarkable ionic conductivity (1.17 × 10^-4 S cm^-1 at room temperature), high Li⁺ transference number (0.77), and a 4.7 V-wide operating window. More impressively, Li⁺-implanted copper maleate hydrate solid-state electrolytes are demonstrated to have exceptional compatibility with both cathode and Li anode, enabling long-term stability of more than 800 cycles. This work brings new insight on exploring superior room-temperature ionic conductors based on metal coordination compounds.

Grants and funding

52122211/National Natural Science Foundation of China (National Science Foundation of China)