Self‐Assembled Ionic Clusters Accelerate Li‐Ion Transport Through Microphase‐Separated Polyelectrolytes

C Cheng‐Dong Fang (State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China) Y Yu‐Hang Zhang (State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China) S Si‐Fan Hu (College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou Jiangsu China) X Xiaodong Lin (Institute of Condensed Matter and Nanosciences) S Shu Zhang P Peng‐Fei Sun (State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China) L Liu‐bin Feng (State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China) J Jian‐Jun Wang (College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou Jiangsu China) A Alexandru Vlad (Institute of Condensed Matter and Nanosciences) J Jia‐Jia Chen (State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China)

Abstract

ABSTRACT Precise, molecular‐level control of ion coordination and mesoscale morphology is essential for pushing solid polymer electrolytes toward the conductivity and mechanical robustness metrics demanded by next‐generation batteries. Here we introduce an elastic microphase polyelectrolyte (EMP) whose thermodynamically driven microphase separation self‐assembles Li + ‐rich ionic clusters. These clusters stitch together a dynamic, percolating conduction network that achieves high ionic conductivity of 2.9 × 10 −4 S cm −1 and a high Li + transference number of 0.67 at room temperature. Operando galvanostatic impedance spectroscopy uncovers a field‐responsive boost in conductivity—from 4.1 × 10 −4 to 1.9 × 10 −3  S cm −1 as the current density increases from 25 to 200 µA cm −2 —evidence of bias‐induced cluster reconfiguration. Mechanically, the EMP combines high elasticity with self‐healing, ensuring intimate, long‐lived electrode contact. When paired with a LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode, solid‐state cells retain 93.92% of their initial capacity after 50 cycles under a high‐capacity loading of ∼2.0 mAh cm −2 . By demonstrating how supramolecular ionic assembly can be harnessed to couple ion transport, mechanics, and electrochemical stability, this work lays a versatile design platform for high‐performance, solid‐state lithium batteries.

Article Details

Volume / Issue Vol. 65, Issue 14
Published March 27, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (10)

C

Cheng‐Dong Fang

State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China

Y

Yu‐Hang Zhang

State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China

S

Si‐Fan Hu

College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou Jiangsu China

X

Xiaodong Lin

Institute of Condensed Matter and Nanosciences

S

Shu Zhang

P

Peng‐Fei Sun

State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China

L

Liu‐bin Feng

State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China

J

Jian‐Jun Wang

College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou Jiangsu China

A

Alexandru Vlad

Institute of Condensed Matter and Nanosciences

J

Jia‐Jia Chen

State Key Laboratory For Physical Chemistry of Solid Surfaces Innovation Laboratory for Sciences and Technologies of Energy Material of Fujian Province (IKKEM) Collaborative Innovation Center of Chemistry for Energy Materials (<i>i</i>ChEM) Engineering Research Center of Electrochemical Technologies of Ministry of Education, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University Xiamen Fujian China