Tunneling Interpenetrative Lithium Ion Conduction Channels in Polymer-in-Ceramic Composite Solid Electrolytes

Lei Zhu; Junchao Chen; Youwei Wang; Wuliang Feng; Yanzhe Zhu; Sander F H Lambregts; Yongmin Wu; Cheng Yang; Ernst R H van Eck; Luming Peng; Arno P M Kentgens; Weiping Tang; Yongyao Xia

doi:10.1021/jacs.3c11988

Tunneling Interpenetrative Lithium Ion Conduction Channels in Polymer-in-Ceramic Composite Solid Electrolytes

J Am Chem Soc. 2024 Mar 13;146(10):6591-6603. doi: 10.1021/jacs.3c11988. Epub 2024 Feb 29.

Authors

Lei Zhu^{1

2}, Junchao Chen^{3

4}, Youwei Wang⁵, Wuliang Feng⁶, Yanzhe Zhu³, Sander F H Lambregts⁴, Yongmin Wu², Cheng Yang², Ernst R H van Eck⁴, Luming Peng⁷, Arno P M Kentgens⁴, Weiping Tang^{2

3

8}, Yongyao Xia^{1

9}

Affiliations

¹ Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan University, Shanghai 200433, China.
² State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China.
³ School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
⁴ Magnetic Resonance Research Center, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen AJ 6525, The Netherlands.
⁵ State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China.
⁶ Institute of Sustainable Energy & College of Science, Shanghai University, Shanghai 200444, China.
⁷ Key Laboratory of Mesoscopic Chemistry of MOE and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, 163 Xianlin Road, Nanjing 210023, China.
⁸ Key Laboratory of Green and High-end Utilization of Salt Lake Resources, Chinese Academy of Sciences, Xining 810008, China.
⁹ Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua 321004, China.

PMID: 38420768
DOI: 10.1021/jacs.3c11988

Abstract

Polymer-in-ceramic composite solid electrolytes (PIC-CSEs) provide important advantages over individual organic or inorganic solid electrolytes. In conventional PIC-CSEs, the ion conduction pathway is primarily confined to the ceramics, while the faster routes associated with the ceramic-polymer interface remain blocked. This challenge is associated with two key factors: (i) the difficulty in establishing extensive and uninterrupted ceramic-polymer interfaces due to ceramic aggregation; (ii) the ceramic-polymer interfaces are unresponsive to conducting ions because of their inherent incompatibility. Here, we propose a strategy by introducing polymer-compatible ionic liquids (PCILs) to mediate between ceramics and the polymer matrix. This mediation involves the polar groups of PCILs interacting with Li⁺ ions on the ceramic surfaces as well as the interactions between the polar components of PCILs and the polymer chains. This strategy addresses the ceramic aggregation issue, resulting in uniform PIC-CSEs. Simultaneously, it activates the ceramic-polymer interfaces by establishing interpenetrating channels that promote the efficient transport of Li⁺ ions across the ceramic phase, the ceramic-polymer interfaces, and the intervening pathways. Consequently, the obtained PIC-CSEs exhibit high ionic conductivity, exceptional flexibility, and robust mechanical strength. A PIC-CSE comprising poly(vinylidene fluoride) (PVDF) and 60 wt % PCIL-coated Li₃Zr₂Si₂PO₁₂ (LZSP) fillers showcasing an ionic conductivity of 0.83 mS cm^-1, a superior Li⁺ ion transference number of 0.81, and an elongation of ∼300% at 25 °C could be produced on meter-scale. Its lithium metal pouch cells show high energy densities of 424.9 Wh kg^-1 (excluding packing films) and puncture safety. This work paves the way for designing PIC-CSEs with commercial viability.