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Insight into the Alkaline Stability of N‐Heterocyclic Ammonium Groups for Anion‐Exchange Polyelectrolytes
Author(s) -
Chen Nanjun,
Jin Yiqi,
Liu Haijun,
Hu Chuan,
Wu Bo,
Xu Shaoyi,
Li Hui,
Fan Jiantao,
Lee Young Moo
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202105231
Subject(s) - chemistry , ion exchange , degradation (telecommunications) , chemical stability , ammonium , ion , polyelectrolyte , inorganic chemistry , organic chemistry , polymer , telecommunications , computer science
The alkaline stability of N‐heterocyclic ammonium (NHA) groups is a critical topic in anion‐exchange membranes (AEMs) and AEM fuel cells (AEMFCs). Here, we report a systematic study on the alkaline stability of 24 representative NHA groups at different hydration numbers ( λ ) at 80 °C. The results elucidate that γ‐substituted NHAs containing electron‐donating groups display superior alkaline stability, while electron‐withdrawing substituents are detrimental to durable NHAs. Density‐functional‐theory calculations and experimental results suggest that nucleophilic substitution is the dominant degradation pathway in NHAs, while Hofmann elimination is the primary degradation pathway for NHA‐based AEMs. Different degradation pathways determine the alkaline stability of NHAs or NHA‐based AEMs. AEMFC durability (from 1 A cm −2 to 3 A cm −2 ) suggests that NHA‐based AEMs are mainly subjected to Hofmann elimination under 1 A cm −2 current density for 1000 h, providing insights into the relationship between current density, λ value, and durability of NHA‐based AEMs.