1 Department of Mechanical and Materials Engineering, University of Western Ontario, London, Ontario, Canada.
2 School of Materials Science and Engineering, Zhejiang University, Hangzhou, People's Republic of China.
3 Department of Chemical and Materials Engineering, Concordia University, Montreal, Quebec, Canada.
4 Eastern Institute for Advanced Study, Eastern Institute of Technology, Nngbo, People's Republic of China.
5 Zhejiang Key Laboratory of All-Solid-State Battery, Ningbo Key Laboratory of All-Solid-State Battery, Ningbo, People's Republic of China.
6 Canadian Light Source Inc., University of Saskatchewan, Saskatoon, Saskatchewan, Canada.
7 Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, People's Republic of China.
8 Institute of Physical Science and Information Technology, Anhui University, Hefei, People's Republic of China.
9 Department of Mechanical and Materials Engineering, University of Western Ontario, London, Ontario, Canada. cwang@eitech.edu.cn.
10 Eastern Institute for Advanced Study, Eastern Institute of Technology, Nngbo, People's Republic of China. cwang@eitech.edu.cn.
11 Zhejiang Key Laboratory of All-Solid-State Battery, Ningbo Key Laboratory of All-Solid-State Battery, Ningbo, People's Republic of China. cwang@eitech.edu.cn.
12 Department of Mechanical and Materials Engineering, University of Western Ontario, London, Ontario, Canada. xsun@eitech.edu.cn.
13 Eastern Institute for Advanced Study, Eastern Institute of Technology, Nngbo, People's Republic of China. xsun@eitech.edu.cn.
14 Zhejiang Key Laboratory of All-Solid-State Battery, Ningbo Key Laboratory of All-Solid-State Battery, Ningbo, People's Republic of China. xsun@eitech.edu.cn.

Organic electrode materials offer a versatile, sustainable approach for next-generation lithium-ion batteries but are limited by low working voltages and poor cycling stability. Here we report a solid-solvation-structure design strategy to improve both the voltage and stability of organic electrode materials in all-solid-state batteries. As a proof of concept, we incorporate halide electrolytes as solid solutes and tetrachloro-o-benzoquinone as a solid solvent to form homogeneous solid cathode solutions. Systematic optimization of the inner solvation configuration enables tetrachloro-o-benzoquinone to achieve a high working voltage (3.6 V vs. Li⁺/Li) at room temperature within an asymmetric solid solvation sheath. Moreover, the equilibrium redox pathway and electrostatically driven self-healing interfaces revealed rapid redox kinetics and stable performance over 7,500 cycles in all-solid-state batteries under low stack pressures. This work demonstrates that organic electrode materials can serve as viable, durable and cost-effective alternatives to transition metal oxides in all-solid-state batteries.