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支化柔性侧链N-螺环基阴离子交换膜研究

作者：刘畅¹，刘晋武¹，杨文溪¹，张帆¹，鞠佳¹，崔珺²，张扬¹

单位： 1. 辽宁石油化工大学石油化工学院，抚顺 113001； 2. 沈阳工学院生命工程学院，抚顺 113000

关键词：阴离子交换膜；支化柔性侧链； N螺环阳离子；燃料电池

DOI号： 10.16159/j.cnki.issn1007-8924.2026.02.009

分类号： TQ028； TM912.1

出版年,卷(期):页码： 2026,46(2):88-95

摘要：

开发兼具高OH-电导率、稳定性及强度的阴离子交换膜（AEMs）是燃料电池领域的研究前沿。尽管N螺环阳离子表现出优异的耐碱性，但其刚性大体积限制OH-传导及成膜性。为此，本研究提出“一锅序列接枝”策略，将支化柔性侧链和N螺环阳离子先后接枝于聚砜（PSf）主链。支化侧链不仅促进构建高效离子通道，更增强了膜的强度与尺寸稳定性；同时，侧链的位阻效应有效提升了AEMs的耐碱性。结果表明，所制膜PSf2C6ASD显示出较高的OH-电导率（141.8 mS/cm，80 ℃）、良好的拉伸强度（45.1 MPa）和尺寸稳定性（溶胀率18.3%，80 ℃)，及优异的耐碱性（80 ℃、1 mol/L KOH中浸泡30 d后，OH-电导率保持率超过96%）。单电池测试中，其开路电压为1.01 V，在80 ℃、2 000 mA/cm2电流密度下的功率密度高达926.2 mW/cm2。

The development of anion exchange membranes (AEMs) that integrate high OH- conductivity, robust stability and mechanical strength represents a forefront research challenge in the fuel cell field. Although N-spirocyclic cations demonstrate exceptional alkaline stability, their rigid and bulky nature often compromises OH- conductivity and membrane-forming properties. To address this, this work proposed a novel “one-pot and sequential grafting” strategy to graft polysulfone (PSf) backbones with branched flexible side chains and N-spirocyclic cations sequentially. The incorporation of branched side chains not only facilitated the formation of efficient ion transport channels, but also enhanced the mechanical strength and dimensional stability of the membranes. Concurrently, the steric hindrance provided by these side chains significantly improved the alkaline stability of the AEMs. The resulting membrane PSf2C6ASD exhibited outstanding comprehensive properties: high OH- conductivity of 141.8 mS/cm at 80 ℃, robust tensile strength of 45.1 MPa, and favorable dimensional stability with a swelling ratio of 18.3% at 80 ℃. Remarkably, it possessed exceptional alkaline stability, retaining over 96% of its original OH- conductivity after being treated in 1 mol/L KOH at 80 ℃ for 30 days. Furthermore, in a single-cell test, the open-circuit voltage of 1.01 V was achieved and the power density reached up to 926.2 mW/cm2 at 80 ℃ with a current density of 2 000 mA/cm2.

基金项目：

国家自然科学基金项目（22408144）；辽宁省教育厅高等学校基本科研项目（青年项目）（JYTQN2023347，JYTQN2023350）；辽宁省科技计划联合计划（自然科学基金-面上项目）（2025-MSLH-458，2025-MSLH-459）；辽宁石油化工大学引进人才科研启动基金资助项目（2023XJJL-010，2023XJJL-011）

作者简介：

刘畅（2001-），男，辽宁彰武人，硕士研究生，研究方向为功能膜材料的制备

参考文献：

[1]Chen N，Hu C，Wang H H，et al. Poly(alkyl-terphenyl piperidinium) ionomers and membranes with an outstanding alkaline-membrane fuel-cell performance of 2.58 W/cm2[J]. Angew Chem Int Ed，2021，60 (14)：7710-7718.
[2]Sriram G，Dhanabalan K，Ajeya K V，et al. Recent progress in anion exchange membranes (AEMs) in water electrolysis: Synthesis, physio-chemical analysis, properties, and applications[J]. J Mater Chem A，2023，11 (39)：20886-21008.
[3]Xiao S，Zhang F，Wang J L，et al. Uneven side-chain cation-modified poly(aryl piperidinium) anion exchange membranes with broadened OH- conducting channels for fuel cells[J]. ACS Sustainable Chem Eng，2025，13(30)：11959-11970.
[4]Yang Q，Cai Y Y，Zhu Z Y，et al. Multiple enhancement effects of crown ether in troger’s base polymers on the performance of anion exchange membranes[J]. ACS Appl Mater Interfaces，2020，12 (22)：24806-24816.
[5]Zeng L，Liao Y，Wang J，et al. Construction of highly efficient ion channel within anion exchange membrane based on interpenetrating polymer network for H2/air (CO2-free) alkaline fuel cell[J]. J Power Sources，2021，486(28)：229377-229384.
[6]Li Z L，Gao L，Liu J，et al. Intrinsic microporous poly(phenyl-alkane)s with pendent piperazinium for high performance anion exchange membrane fuel cells[J]. J Membr Sci，2024，700：122673-122678.
[7]Zhang J J，Zhang K Y，Liang X，et al. Self-aggregating cationic-chains enable alkaline stable ion-conducting channels for anion-exchange membrane fuel cells[J]. J Mater Chem A，2021，9(1)：327-337.
[8]Gong S T，Liu A M，Qaisrani N A，et al. Completely methylene-free side chain enables significant microphase separation at medium IECs for fuel-cell anion exchange membranes[J]. ACS Appl Mater Interfaces，2024，16 (21)：27741-27749.
[9]Zhang Q，Zhang Q F，Wang J H，et al. Synthesis and alkaline stability of novel cardo poly(aryl ether sulfone)s with pendent quaternary ammonium aliphatic side chains for anion exchange membranes[J]. Polymer，2010，51(23)：5407-5416.
[10]Marino M G, Kreuer K D. Alkaline stability of quaternary ammonium cations for alkaline fuel cell membranes and ionic liquids[J]. ChemSusChem，2015，8(3)：513-523.
[11]Pham T H，Olsson J S, Jannasch P. Effects of the N-alicyclic cation and backbone structures on the performance of poly(terphenyl)-based hydroxide exchange membranes[J]. J Mater Chem A，2019，7(26)：15895-15906.
[12]Gu L，Dong H，Sun Z，et al. Spirocyclic quaternary ammonium cations for alkaline anion exchange membrane applications: An experimental and theoretical study[J]. RSC Adv，2016，6(97)：94387-94398.
[13]Wang Y，Wang S，Sui Z Y，et al. “Fishbone” design of amino/N-spirocyclic cations toward high-performance poly(triphenylene piperidine) anion-exchange membranes for fuel cells[J]. ACS Appl Mater Interfaces，2024，16(3)：4003-4012.
[14]Chu S G，Gu Y M，Wang Y，et al. Poly(isatin biphenylene) anion exchange membranes based on functionalization of long side chain N-spirocyclic[J]. Mater Today Chem，2024，42：102396-102404.
[15]Wang S，Wang Z，Xu J M，et al. Construction of N-spirocyclic cationic three-dimensional highly stable transport channels by electrospinning for anion exchange membrane fuel cells[J]. J Membr Sci，2022，660：120852-120861.
[16]Chen N，Long C，Li Y，et al. Ultrastable and high ion-conducting polyelectrolyte based on six-membered N-spirocyclic ammonium for hydroxide exchange membrane fuel cell applications[J]. ACS Appl Mater Interfaces，2018，10(18)：15720-15732.
[17]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]. J Membr Sci，2019，578：239-259.
[18]Bakvand P M，Pham T H and Jannasch P. N-Spirocyclic quaternary ammonium ionene membranes prepared by polyhydroxyalkylation[J]. J Membr Sci，2025，723：123922-123933.
[19]Gong X，He G H，Yan X M，et al. Electrospun nanofiber enhanced imidazolium functionalized polysulfone composite anion exchange membranes[J]. RSC Adv，2015，5(115)：95118-95125.
[20]Zhang Y，Chen W T，Yan X M，et al. Ether spaced N-spirocyclic quaternary ammonium functionalized crosslinked polysulfone for high alkaline stable anion exchange membranes[J]. J Membr Sci，2020，598： 117650-117660.
[21]Liu D，Lin L M，Xie Y J，et al. Anion exchange membrane based on poly(arylene ether ketone) containing long alkyl densely quaternized carbazole derivative pendant[J]. J Membr Sci，2021，623：119079-119087.
[22]Du X M，Zhang H Y，Yuan Y J，et al. Constructing micro-phase separation structure to improve the performance of anion-exchange membrane based on poly(aryl piperidinium) cross-linked membranes[J]. J Power Sources，2021，487(1)：229429-229439.
[23]朱兆宇，张秋根，朱爱梅，等. 萘基侧链型阴离子交换膜的制备[J]. 膜科学与技术，2022，42(1)：33-40.
[24]Zhang Y，Chen W T，Li T T，et al. A rod-coil grafts strategy for N-spirocyclic functionalized anion exchange membranes with high fuel cell power density[J]. J Power Sources，2021，490(1)：229544-229554.
[25]Xu G D，Pan J，Zou X Y，et al. High-performance poly(biphenyl piperidinium) type anion exchange membranes with interconnected ion transfer channels: Cooperativity of dual cations and fluorinated side chains[J]. Adv Funct Mater，2023，33(35)：2302364-2302373.

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