Missing-Linker Defect Functionalized Metal–Organic Frameworks Accelerating Zinc Ion Conduction for Ultrastable All-Solid-State Zinc Metal Batteries

• Published in: ACS nano Vol. 18; no. 36; pp. 25237 - 25248
• Main Authors: Hui, Xiaobin, Zhan, Zhen, Zhang, Zeyu, Yu, Jingya, Jiang, Pengyan, Dang, Zhengzheng, Wang, Jian, Cai, Songhua, Wang, Yanming, Xu, Zheng-Long
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10-09-2024
• Subjects: Zn-ion battery; competitive coordination; solid-state electrolyte; single-ion conducting; defected MOF
• ISSN: 1936-0851; 1936-086X; 1936-086X
• DOI: 10.1021/acsnano.4c07907

Solid-state polymer electrolytes (SPEs) are promising for high-performance zinc metal batteries (ZMBs), but they encounter critical challenges of low ionic conductivity, limited Zn2+ transference number (t Zn2+), and an unstable electrolyte-electrode interface. Here, we present an effective approach involving a missing-linker metallic organic framework (MOF)-catalyzed poly­(ethylene glycol) diacrylate (PEGDA)/polyacrylamide (PAM) copolymer SPE for single Zn2+ conduction and seamless electrolyte-electrode contact. The single-Zn2+ conduction is facilitated by the anchoring of the OTF– anions onto the unsaturated metal sites of missing-linker MOF, while the PEGDA and PAM chains in competitive coordination with Zn2+ ions promote rapid Zn ion transport. Our all-solid-state electrolyte simultaneously achieves a superior ionic conductivity of 1.52 mS cm–1 and a high t Zn2+ of 0.83 at room temperature, alongside uniform Zn metal deposition (1000 cycles in symmetric cells) and high Zn plating/striping efficiencies (>99% after 600 cycles in asymmetric cells). Applications of our SPE in Zn//VO2 full cells are further demonstrated with a long lifespan of 2000 cycles and an extremely low-capacity degradation rate of 0.012% per cycle. This work provides an effective strategy for using a missing-linker MOF to catalyze competitively coordinating copolymers for accelerating Zn2+ ion conduction, assisting the future design of all-solid-state ZMBs.