Anion exchange membranes based on poly (ether ether ketone) containing N-spirocyclic quaternary ammonium cations in phenyl side chain

• Published in: International journal of hydrogen energy 2021-05, Vol.46 (36), p.19116-19128
• Main Authors: Shang, Lichao, Yao, Dan, Pang, Bohao, Zhao, Chengji
• Format: Article
• Language: English
• Subjects: AEMs; Alkaline fuel cells; N-spirocyclic QA groups; Poly (ether ether ketone)s
• ISSN: 0360-3199; 1879-3487
• DOI: 10.1016/j.ijhydene.2021.03.059

It was reported that the existence of N-spirocyclic quaternary ammonium (QA) cation could improve alkaline stability of anion exchange membrane materials (AEM). Therefore, the cyclo-quaternization reaction with pyrrolidine (Pyr) and piperidine (Pip) was carried out to prepare quaternized poly (ether ether ketone)s bearing five-membered and six-membered N-spirocyclic quaternary ammonium (QA) groups in the phenyl side chains (QPEEK-spiro-pyr and QPEEK-spiro-pip), respectively. From the transmission electron microscope, the hydrophilic-hydrophobic phase-separated morphology was formed in QPEEK-spiro membranes after incorporating N-spirocyclic QA cations and bulky spacer simultaneously in the phenyl side chain. The effect of N-spirocyclic QA groups on performance of resulted AEMs was then studied in detail. The anion conductivities of QPEEK-spiro-pyr and QPEEK-spiro-pip in OH− form at 80 °C were 49.6 and 30.9 S cm−1, respectively. The remaining proportions of hydroxide conductivity for QPEEK-spiro-pyr and QPEEK-spiro-pip membranes after immersing in 1 M NaOH at 60 °C were 81.0% and 74.7%, respectively, which were higher than that of 62.3% for QPEEK-TMA containing conventional QA groups in the phenyl side chain. Fuel cell assembled with QPEEK-spiro-pyr achieves a peak power density of 90 mW cm−2. These results indicate the strategy of simultaneously introducing N-spirocyclic QA cations and bulky spacers can improve the performance of AEM to a certain extent. There are some other factors that influence the alkaline stability of the prepared AEMs, such as the existence of ether bonds in the main chain. However, this work still provides a valuable reference towards the molecular design of AEMs with improved performance. •QPEEK-spiro AEMs showed good thermal stability and sufficient mechanical strength.•The bulky N-spirocyclic QA cations was proposed to enhance the alkaline stability.•QPEEK-spiro-pyr showed the highest anion conductivity of 49.6 at 80 °C.•The clear phase separation morphology was formed in QPEEK-spiro membranes.