Superior Room‐Temperature Anhydrous Proton Conduction in 3D Porous Benzimidazole Membranes Enabled by Strong Acid Confinement

J Jin Zhang N Nianyu Zhao (State Key Laboratory of Materials‐Oriented Chemical Engineering and College of Chemistry and Molecular Engineering Nanjing Tech University Nanjing 211816 P. R. China) Q Qian Liu S Siyao Li (State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, No.130 Meilong Road, Shanghai, 200237, P. R. China) L Linzhou Zhuang (State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, No.130 Meilong Road, Shanghai, 200237, P. R. China) Q Qiao Qiao (Department of Chemistry) D Dongsheng Shao (School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore) X Xiao‐Ming Ren (State Key Laboratory of Materials‐Oriented Chemical Engineering and School of Chemistry and Molecular Engineering Nanjing Tech University Nanjing China) Z Zhi Xu (State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, No.130 Meilong Road, Shanghai, 200237, P. R. China)

Abstract

Abstract Phosphoric acid‐doped polybenzimidazole (PA‐PBI) is a leading anhydrous proton exchange membrane (APEM) material for non‐aqueous electrochemical technologies. However, its flexible linear backbone results in poorly defined and acid‐sensitive proton conduction pathways, compromising durability and limiting the use of stronger acids for conductivity enhancement. To overcome these limitations, we designed and synthesized a novel self‐standing, 3D benzimidazole‐functionalized covalent triazine framework membrane (OBI‐CTFM) via a sol–gel approach. This membrane exhibits exceptional mechanical strength, strong acid resistance, and an intrinsic microporous structure with alkaline imidazole groups that enable effective acid uptake and confinement. Remarkably, the methanesulfonic acid‐treated membrane (MSA@OBI‐CTFM) achieved a record‐high anhydrous proton conductivity (>10 −2 S cm −1 ) near room temperature, surpassing most reported anhydrous proton conductors. As an APEM in proton batteries, this membrane enabled remarkable cycling stability (∼7000 cycles) and high specific capacity. Our work demonstrates the critical role of 3D porous structures in APEMs and paves the way for advanced PBI membranes in electrochemical applications.

Article Details

Volume / Issue Vol. 65, Issue 4
Published January 22, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (9)

J

Jin Zhang

N

Nianyu Zhao

State Key Laboratory of Materials‐Oriented Chemical Engineering and College of Chemistry and Molecular Engineering Nanjing Tech University Nanjing 211816 P. R. China

Q

Qian Liu

S

Siyao Li

State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, No.130 Meilong Road, Shanghai, 200237, P. R. China

L

Linzhou Zhuang

State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, No.130 Meilong Road, Shanghai, 200237, P. R. China

Q

Qiao Qiao

Department of Chemistry

D

Dongsheng Shao

School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore

X

Xiao‐Ming Ren

State Key Laboratory of Materials‐Oriented Chemical Engineering and School of Chemistry and Molecular Engineering Nanjing Tech University Nanjing China

Z

Zhi Xu

State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, No.130 Meilong Road, Shanghai, 200237, P. R. China