Bilayer Zwitterionic Metal-Organic Framework for Selective All-Solid-State Superionic Conduction in Lithium Metal Batteries

Yuan Ouyang; Wei Gong; Qi Zhang; Jia Wang; Sijia Guo; Yingbo Xiao; Dixiong Li; Changhong Wang; Xueliang Sun; Chaoyang Wang; Shaoming Huang

doi:10.1002/adma.202304685

Bilayer Zwitterionic Metal-Organic Framework for Selective All-Solid-State Superionic Conduction in Lithium Metal Batteries

Adv Mater. 2023 Sep;35(39):e2304685. doi: 10.1002/adma.202304685. Epub 2023 Jul 28.

Authors

Yuan Ouyang¹, Wei Gong¹, Qi Zhang¹, Jia Wang¹, Sijia Guo¹, Yingbo Xiao¹, Dixiong Li¹, Changhong Wang², Xueliang Sun², Chaoyang Wang³, Shaoming Huang^{1

4}

Affiliations

¹ Guangzhou Key Laboratory of Low-Dimensional Materials and Energy Storage Devices, Guangdong University of Technology, Guangzhou, 510006, China.
² Department of Mechanical and Materials Engineering, University of Western Ontario, 1151 Richmond St., London, ON, N6A 3K7, Canada.
³ Electrochemical Engine Center (ECEC) and Department of Mechanical Engineering, Pennsylvania State University, University Park, PA, USA.
⁴ College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, No. 2318 Yuhangtang Rd., Cangqian, Yuhang District, Hangzhou, China.

PMID: 37344893
DOI: 10.1002/adma.202304685

Abstract

Solid-state batteries (SSBs) hold immense potential for improved energy density and safety compared to traditional batteries. However, existing solid-state electrolytes (SSEs) face challenges in meeting the complex operational requirements of SSBs. This study introduces a novel approach to address this issue by developing a metal-organic framework (MOF) with customized bilayer zwitterionic nanochannels (MOF-BZN) as high-performance SSEs. The BZN consist of a rigid anionic MOF channel with chemically grafted soft multicationic oligomers (MCOs) on the pore wall. This design enables selective superionic conduction, with MCOs restricting the movement of anions while coulombic interaction between MCOs and anionic framework promoting the dissociation of Li⁺ . MOF-BZN exhibits remarkable Li⁺ conductivity (8.76 × 10^-4 S cm^-1 ), high Li⁺ transference number (0.75), and a wide electrochemical window of up to 4.9 V at 30 °C. Ultimately, the SSB utilizing flame retarded MOF-BZN achieves an impressive specific energy of 419.6 Wh kg_{anode+cathode+electrolyte} ^-1 under constrained conditions of high cathode loading (20.1 mg cm^-2 ) and limited lithium metal source. The constructed bilayer zwitterionic MOFs present a pioneering strategy for developing advanced SSEs for highly efficient SSBs.

Keywords: all-solid-state batteries; bilayer zwitterionic nanochannels; ion conduction; metal-organic frameworks; solid-state electrolytes.

Abstract

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