Abstract
In order to effectively improve the properties of anion exchange membrane (AEM) materials, a series of novel poly(aryl ether nitrile)s with flexible side-chain-type quaternary phosphonium cations (PAEN-TPP-x) were designed and prepared on the basis of considering the influences of polymer backbone, cationic group species and the connection way between the cations and polymer chains. The synthetic method, structure and ion-exchange capacity, water absorption, swelling, hydroxide conductivity and alkaline stability of the obtained AEMs were studied. A comparative study with other reported AEMs was also performed for further exploration of the relationship between the structure and properties. These AEMs with flexible side-chain-type quaternary phosphonium cations displayed good comprehensive properties. Their water uptakes and swelling ratios were in the range of 11.6%–22.7% and 4.4%–7.8% at 60°C, respectively. They had hydroxide conductivity in the range of 28.6–45.8 mS cm−1 at 60°C. Moreover, these AEMs also exhibited improved alkaline stability, and the hydroxide conductivity for PAEN-TPP-0.35 could remain 82.1% and 80.6% of its initial value at 60 and 90°C in 2 mol L−1 NaOH solution for 480 h, respectively.
摘要
为有效改善聚合物阴离子交换膜材料(AEMs)的性能, 本研究在综合考虑聚合物结构、离子官能团种类及其链接方式对AEMs影响的基础上, 设计制备了一系列含有柔性侧链型季鏻阳离子结构的新型聚芳醚腈(PAEN-TPP-x)阴离子交换膜. 分别对所制聚芳醚腈阴离子交换膜的合成方法、结构和离子交换容量、吸水率、溶胀率、氢氧化物电导率及碱稳定性进行了系统研究, 并与一些其他已报道的AEMs进行了比较研究, 以进一步探索其结构与性能之间的关系. 研究发现所制备的含有柔性侧链型季鏻阳离子结构的聚芳醚腈阴离子交换膜具有良好的综合性能 在60°C下, 它们的吸水率、溶胀率和离子传导率分别为11.6%–22.7%, 4.4%–7.8%和28.6–45.8 mS cm−1. 与此同时, 该类AEMs还表现出良好的碱性稳定性, 其中代表性样品PAEN-TPP-0.35在2 mol L−1 NaOH溶液中、60和90°C下浸泡480 h后的OH−传导率分别保持在其初始值的82.1%和80.6%.本研究可为高性能聚合物阴离子交换膜材料的设计制备和改性提供新的思路和方法.
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References
Miyake J, Kusakabe M, Tsutsumida A, et al. Remarkable reinforcement effect in sulfonated aromatic polymers as fuel cell membrane. ACS Appl Energy Mater, 2018, 1: 1233–1238
Zhang J, He Y, Liang X, et al. Towards the gemini cation anion exchange membranes by nucleophilic substitution reaction. Sci China Mater, 2019, 62: 973–981
Chen Y, Liu Z, Lin M, et al. Selectivity enhancement of quaternized poly(arylene ether ketone) membranes by ion segregation for vanadium redox flow batteries. Sci China Chem, 2019, 62: 479–490
Zhang S, Zhang B, Chen Y, et al. Preparation and properties of quaternized poly(phthalazinone ether ketone ketone) anion-exchange membrane for all-vanadium redox flow battery. Chin Sci Bull, 2019, 64: 187–193
Chen Y, Lin Q, Zheng Y, et al. Densely quaternized anion exchange membranes synthesized from Ullmann coupling extension of ionic segments for vanadium redox flow batteries. Sci China Mater, 2019, 62: 211–224
Wang C, Zhou Y, Shen B, et al. Proton-conducting poly(ether sulfone ketone)s containing a high density of pendant sulfonic groups by a convenient and mild post-sulfonation. Polym Chem, 2018, 9: 4984–4993
Wang C, Shen B, Zhou Y, et al. Sulfonated aromatic polyamides containing nitrile groups as proton exchange fuel cell membranes. Int J Hydrogen Energy, 2015, 40: 6422–6429
Zhang X, Chu X, Zhang M, et al. Molecularly designed, solvent processable tetraalkylammonium-functionalized fluoropolyolefin for durable anion exchange membrane fuel cells. J Membrane Sci, 2019, 574: 212–221
Wang C, Zhou Y, Xu C, et al. Synthesis and properties of new side-chain-type poly(arylene ether sulfone)s containing tri-imidazole cations as anion-exchange membranes. Int J Hydrogen Energy, 2018, 43: 20739–20749
Hossain MM, Wu L, Liang X, et al. Anion exchange membrane crosslinked in the easiest way stands out for fuel cells. J Power Sources, 2018, 390: 234–241
Kwasny MT, Zhu L, Hickner MA, et al. Thermodynamics of counterion release is critical for anion exchange membrane conductivity. J Am Chem Soc, 2018, 140: 7961–7969
Mandal M, Huang G, Kohl PA. Highly conductive anion-exchange membranes based on cross-linked poly(norbornene): Vinyl addition polymerization. ACS Appl Energy Mater, 2019, 2: 2447–2457
Liu L, Chu X, Li N. Recent development in polyolefin-based anion exchange membrane for fuel cell application. Chin Sci Bull, 2019, 64: 123–133
Zheng XY, Song SY, Yang JR, et al. 4-Formyl dibenzo-18-crown-6 grafted polyvinyl alcohol as anion exchange membranes for fuel cell. Eur Polym J, 2019, 112: 581–590
Ryu J, Seo JY, Choi BN, et al. Quaternized chitosan-based anion exchange membrane for alkaline direct methanol fuel cells. J Industrial Eng Chem, 2019, 73: 254–259
Lim H, Lee B, Yun D, et al. Poly(2,6-dimethyl-1,4-phenylene oxide)s with various head groups: Effect of head groups on the properties of anion exchange membranes. ACS Appl Mater Interfaces, 2018, 10: 41279–41292
Xing Y, Liu L, Wang C, et al. Side-chain-type anion exchange membranes for vanadium flow battery: Properties and degradation mechanism. J Mater Chem A, 2018, 6: 22778–22789
Zhang Z, Xiao X, Yan X, et al. Highly conductive anion exchange membranes based on one-step benzylation modification of poly(ether ether ketone). J Membrane Sci, 2019, 574: 205–211
Lee WH, Mohanty AD, Bae C. Fluorene-based hydroxide ion conducting polymers for chemically stable anion exchange membrane fuel cells. ACS Macro Lett, 2015, 4: 453–457
Sana B, Das A, Jana T. Polybenzimidazole as alkaline anion exchange membrane with twin hydroxide ion conducting sites. Polymer, 2019, 172: 213–220
Fan J, Wright AG, Britton B, et al. Cationic polyelectrolytes, stable in 10 M KOHaq at 100°C. ACS Macro Lett, 2017, 6: 1089–1093
Oh BH, Kim AR, Yoo DJ. Profile of extended chemical stability and mechanical integrity and high hydroxide ion conductivity of poly(ether imide) based membranes for anion exchange membrane fuel cells. Int J Hydrogen Energy, 2019, 44: 4281–4292
Yang Z, Guo R, Malpass-Evans R, et al. Highly conductive anion-exchange membranes from microporous Tröger’s base polymers. Angew Chem Int Ed, 2016, 55: 11499–11502
Hu C, Zhang Q, Lin C, et al. Multi-cation crosslinked anion exchange membranes from microporous Tröger’s base copolymers. J Mater Chem A, 2018, 6: 13302–13311
Akiyama R, Yokota N, Miyatake K. Chemically stable, highly anion conductive polymers composed of quinquephenylene and pendant ammonium groups. Macromolecules, 2019, 52: 2131–2138
Olsson JS, Pham TH, Jannasch P. Tuning poly(arylene piper-idinium) anion-exchange membranes by copolymerization, partial quaternization and crosslinking. J Membrane Sci, 2019, 578: 183–195
Wang C, Shen B, Xu C, et al. Side-chain-type poly(arylene ether sulfone)s containing multiple quaternary ammonium groups as anion exchange membranes. J Membrane Sci, 2015, 492: 281–288
Zhao C, Bu F, Na H. Preparation and properties of anion exchange membranes based on multiple quaternary ammonium groups. Chin Sci Bull, 2019, 64: 172–179
Chu X, Liu L, Huang Y, et al. Practical implementation of bis-six-membered N-cyclic quaternary ammonium cations in advanced anion exchange membranes for fuel cells: Synthesis and durability. J Membrane Sci, 2019, 578: 239–250
Hu M, Ding L, Shehzad MA, et al. Comb-shaped anion exchange membrane with densely grafted short chains or loosely grafted long chains? J Membrane Sci, 2019, 585: 150–156
Wang C, Xu C, Shen B, et al. Stable poly(arylene ether sulfone)s anion exchange membranes containing imidazolium cations on pendant phenyl rings. Electrochim Acta, 2016, 190: 1057–1065
Liu Y, Zhang B, Kinsinger CL, et al. Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation. J Membrane Sci, 2016, 506: 50–59
Han H, Ma H, Yu J, et al. Preparation and performance of novel tetraphenylphosphonium-functionalized polyphosphazene membranes for alkaline fuel cells. Eur Polym J, 2019, 114: 109–117
Jang H, Hossain MA, Sutradhar SC, et al. Anion conductive tetra-sulfonium hydroxides poly(fluorenylene ether sulfone) membrane for fuel cell application. Int J Hydrogen Energy, 2017, 42: 12759–12767
Xue B, Wang F, Zheng J, et al. Highly stable polysulfone anion exchange membranes incorporated with bulky alkyl substituted guanidinium cations. Mol Syst Des Eng, 2019, 4: 1039–1047
Zhu T, Xu S, Rahman A, et al. Cationic metallo-polyelectrolytes for robust alkaline anion-exchange membranes. Angew Chem Int Ed, 2018, 57: 2388–2392
Gu S, Wang J, Kaspar RB, et al. Permethyl cobaltocenium (Cp*2Co+) as an ultra-stable cation for polymer hydroxide-exchange membranes. Sci Rep, 2015, 5: 11668
Gao L, Wu X, Yan X, et al. Alkali stability of anion exchange membrane. Chin Sci Bull, 2019, 64: 145–152
Gu S, Cai R, Luo T, et al. A soluble and highly conductive ionomer for high-performance hydroxide exchange membrane fuel cells. Angew Chem Int Ed, 2009, 48: 6499–6502
Akiyama R, Yokota N, Otsuji K, et al. Structurally well-defined anion conductive aromatic copolymers: Effect of the side-chain length. Macromolecules, 2018, 51: 3394–3404
Arges CG, Zhang L. Anion exchange membranes’ evolution toward high hydroxide ion conductivity and alkaline resiliency. ACS Appl Energy Mater, 2018, 1: 2991–3012
Shin DW, Guiver MD, Lee YM. Hydrocarbon-based polymer electrolyte membranes: Importance of morphology on ion transport and membrane stability. Chem Rev, 2017, 117: 4759–4805
Dang HS, Jannasch P. Exploring different cationic alkyl side chain designs for enhanced alkaline stability and hydroxide ion conductivity of anion-exchange membranes. Macromolecules, 2015, 48: 5742–5751
Zheng J, Zhang Q, Qian H, et al. Self-assembly prepared anion exchange membranes with high alkaline stability and organic solvent resistance. J Membrane Sci, 2017, 522: 159–167
Yan X, Gu S, He G, et al. Quaternary phosphonium-functionalized poly(ether ether ketone) as highly conductive and alkali-stable hydroxide exchange membrane for fuel cells. J Membrane Sci, 2014, 466: 220–228
Papakonstantinou P, Deimede V. Self-cross-linked quaternary phosphonium based anion exchange membranes: Assessing the influence of quaternary phosphonium groups on alkaline stability. RSC Adv, 2016, 6: 114329–114343
Tang H, Li D, Li N, et al. Anion conductive poly(2,6-dimethyl phenylene oxide)s with clicked bulky quaternary phosphonium groups. J Membrane Sci, 2018, 558: 9–16
Arges CG, Parrondo J, Johnson G, et al. Assessing the influence of different cation chemistries on ionic conductivity and alkaline stability of anion exchange membranes. J Mater Chem, 2012, 22: 3733–3744
Fang M, Liu D, Neelakandan S, et al. Side-chain effects on the properties of highly branched imidazolium-functionalized copolymer anion exchange membranes. Appl Surf Sci, 2019, 493: 1306–1316
Gottesfeld S, Dekel DR, Page M, et al. Anion exchange membrane fuel cells: Current status and remaining challenges. J Power Sources, 2018, 375: 170–184
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21404016), the Key Research Program of Jiangsu Province (BE2017645), the Six Talent Peaks Project of Jiangsu Province (XCL-078), and a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions of China.
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Wang C designed the experiments, Tao Z performed the experiments, Wang C and Tao Z analyzed the data and wrote the paper. All authors contributed to the general discussion.
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The authors declare that they have no conflict of interest.
Chenyi Wang is an associate professor at the School of Materials Science and Engineering, Changzhou University. He obtained his PhD from Donghua University in 2010. After that, he went to Hanyang University (The Republic of Korea, 2010–2012) as a postdoctoral fellow. His research involves the development of high-performance polymeric materials for fuel cells, flow batteries, and microelectronics devices.
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Wang, C., Tao, Z., Zhao, X. et al. Poly(aryl ether nitrile)s containing flexible side-chain-type quaternary phosphonium cations as anion exchange membranes. Sci. China Mater. 63, 533–543 (2020). https://doi.org/10.1007/s40843-019-1222-x
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DOI: https://doi.org/10.1007/s40843-019-1222-x