Enhancing Ionic Transport at Primary Interparticle Boundaries of Polycrystalline Lithium‐Rich Oxide in All‐Solid‐State Batteries

L Lin Yuan (State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering) W Wenjie Peng Z Ziyang Zhan (National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China) J Jindan Wang (National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China) Y Yiman Feng (National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China) Y Yucen Yan (National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China) R Ruizhi Yu (Institute of Micro/Nano Materials and Devices Ningbo University of Technology Ningbo Zhejiang 315211 P.R. China) C Changhong Wang Z Zhixing Wang (Center for Alloy Innovation and Design, Center for Advancing Materials Performance from the Nanoscale and Hysitron Applied Research Center in China, State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi’an Jiaotong University) H Huajun Guo (National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China) G Guochun Yan (National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China) G Guangchao Li (Department of Applied Biology and Chemical Technology) H Hui Duan J Jiexi Wang X Xueliang Sun

Abstract

Abstract Polycrystalline lithium‐rich oxide (PLRO) is a promising high‐capacity cathode for next‐generation all‐solid‐state batteries (ASSBs). However, its full potential is hindered by sluggish Li + transport at primary interparticle boundaries, mainly due to the limited flowability of inorganic solid‐state electrolytes (SEs). Additionally, infiltrating conventional SEs into PLRO can lead to severe interfacial side reactions because of high melting points. Herein, we report a one‐step, low‐temperature (<200 °C) co‐sintering process that simultaneously synthesizes the SE and infiltrates it into the primary interparticle boundaries of PLRO, creating an integrated composite cathode for ASSBs. This process forms a continuous Li + transport network, enabling deep bulk activation of PLRO. Meanwhile, the co‐sintering process modulates the energy bands of the antibonding transition metal 3d‐O 2p and nonbonding O 2p at the surface, achieving greater orbital overlap to suppress oxygen release and mitigate interfacial phase transformation. As a result, the PLRO‐based ASSBs exhibit an impressive discharge capacity of 271 mAh g −1 at 0.1C, 212 mAh g −1 at 0.5C, and retain 80.0% capacity after 150 cycles. This study highlights the importance of enhancing ion transport to maximize the performance of PLRO‐based ASSBs, offering a practical solution for advancing energy storage technologies.

Article Details

Volume / Issue Vol. 64, Issue 46
Published November 10, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (15)

L

Lin Yuan

State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering

W

Wenjie Peng

Z

Ziyang Zhan

National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China

J

Jindan Wang

National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China

Y

Yiman Feng

National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China

Y

Yucen Yan

National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China

R

Ruizhi Yu

Institute of Micro/Nano Materials and Devices Ningbo University of Technology Ningbo Zhejiang 315211 P.R. China

C

Changhong Wang

Z

Zhixing Wang

Center for Alloy Innovation and Design, Center for Advancing Materials Performance from the Nanoscale and Hysitron Applied Research Center in China, State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi’an Jiaotong University

H

Huajun Guo

National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China

G

Guochun Yan

National Energy Metal Resources and New Materials Key Laboratory Engineering Research Center of the Ministry of Education for Advanced Battery Materials Hunan Provincial Key Laboratory of Nonferrous Value‐Added Metallurgy School of Metallurgy and Environment Central South University Changsha 410083 P.R. China

G

Guangchao Li

Department of Applied Biology and Chemical Technology

H

Hui Duan

J

Jiexi Wang

X

Xueliang Sun