Cyclodextrin Crosslinked Poly (Triphenyl Fluorene Piperidine) Anion Exchange Membrane

doi:10.12422/j.issn.1672-6952.2024.06.004

Abstract

Abstract:

Poly (arylpiperidine) anion exchange membrane (AEM) has been widely studied in anion exchange membrane fuel cells (AEMFCs) and alkaline electrolyzed water due to their excellent alkali resistance and stability. In this work, poly (triphenyl fluorene piperidine) (PTDP) AEM was prepared from 9,9?diphenylfluorene monomer with distorted large volume structure, and hydrophilic large volume cyclodextrin crosslinking agent (β?CD?Br₇) was introduced on this basis, which can control the microphase separation structure in AEMs. The prepared qPTDP?10?CD₅ AEM with 5% crosslinker content reached a high conductivity (130.2 mS/cm at 80 ℃). After the membrane was treated in 1 mol/L NaOH at 80 ℃ for 2 000 h, its conductivity retention was 94.3%, showing good stability. The H₂/O₂ fuel cell assembled with qPTDP?10?CD₅ yielded a peak power density of 1 490 mW/cm² at 80 ℃. In the durability test, the fuel cell assembled with qPTDP?10?CD₅ showed a voltage retention rate of 89.7% after 30 h, showing good cell performance.

Key words: Anion exchange membrane, Twisted massive structure, Bromo?β?cyclodextrin, Cross?linked, Microphase separation, Fuel cell

摘要：

聚芳基哌啶阴离子交换膜（AEM）具有优异的耐碱稳定性，在阴离子交换膜燃料电池和碱性电解水中得到了广泛的研究。利用扭曲大体积结构的9,9?二苯基芴单体，制备了聚(三联苯?芴?哌啶)阴离子交换膜（PTDP）；在此基础上，引入溴化改性的亲水大体积环糊精交联剂（β?CD?Br₇），利用二者共同调控了AEM内的微相分离结构，并进行了性能测试。结果表明，当温度为80 ℃时，交联剂质量分数为5%的qPTDP?10?CD₅ AEM的电导率为130.2 mS/cm；在温度为80 ℃的1 mol/L NaOH溶液中浸泡2 000 h后，其电导率保持率为94.3%，表现出较好的稳定性；当温度为80 ℃时，采用qPTDP?10?CD₅膜组装的氢氧燃料电池表现出1 490 mW/cm²的峰值功率密度；在电池耐久性测试中，采用qPTDP?10?CD₅膜组装的燃料电池经30 h后，电压保留率为89.7%，表现出良好的电池性能。

关键词: 阴离子交换膜, 扭曲大体积结构, 溴?β?环糊精, 交联, 微相分离, 燃料电池

CLC Number:

TQ152

Xinli ZHANG, Long HAN, Shoutao GONG, Fengxiang ZHANG. Cyclodextrin Crosslinked Poly (Triphenyl Fluorene Piperidine) Anion Exchange Membrane[J]. Journal of Liaoning Petrochemical University, 2024, 44(6): 23-31.

张鑫莉, 韩龙, 巩守涛, 张凤祥. 环糊精交联的聚(三联苯⁃芴⁃哌啶)阴离子交换膜的制备[J]. 辽宁石油化工大学学报, 2024, 44(6): 23-31.

Figures/Tables 13

Fig.1 1H NMR spectra of PTDP?x and qPTDP?x

Fig.2 FT?IR spectra of β?CD, qPTDP?10 and qPTDP?10?CD5

Fig.3 TEM images of qPTP, qPTDP?x and qPTDP?10?CD5

Fig.4 SAXS spectrums of qPTDP?10 and qPTDP?10?CD5

Table 1 Free volume properties of qPTP and qPTDP?10

膜样品

V_表/

(cm³·g^-1)

V_骨/

(cm³·g^-1)

Table 2 Water absorption, swelling rate, and ion exchange capacity of qPTP, qPTDP?x and qPTDP?10?CD5 at 30 ℃

膜样品	吸水率/%	溶胀率/%	离子交换容量/(mmol·g^-1)
qPTP	48.7	17.4	2.58
qPTDP⁃5	70.0	26.8	2.57
qPTDP⁃10	90.8	30.7	2.54
qPTDP⁃20	92.5	32.9	2.48
qPTDP⁃10⁃CD₅	78.7	22.6	2.38

Fig.5 Temperature dependent curves of water absorption and swelling rates of qPTP, qPTDP?x and qPTDP?10?CD5

Fig.6 Conductivity and Arrhenius curves of qPTP, qPTDP?x and qPTDP?10?CD5 at different temperatures

Fig.7 Mechanical properties of qPTDP?x and qPTDP?10?CD5 in dry and wet states

Fig.8 Alkali stability of qPTDP?10 and qPTDP?10?CD5

Fig.9 1H NMR spectra of qPTDP?10 under different alkaline treatment times

Fig.10 Polarization and power density curves of H2/O2 fuel cells assembled with qPTDP?10 and qPTDP?10?CD5

Fig.11 Durability of qPTDP?10?CD5 cells

References 21

1	GOKULAPRIYAN R， KIM B H， VIJAYAPRADEEP S， et al. Synthesis of poly N⁃aryl piperidinium membrane and ionomer for anion exchange membrane fuel cell applications［J］. Journal of Membrane Science， 2024， 700： 122692.
2	GUO M L， WANG Z H， XU Y F， et al. Vinyl⁃based in⁃situ crosslinked polybenzimidazoles for anion exchange membranes water electrolysis［J］. Journal of Membrane Science， 2024， 707： 123026.
3	QIAO X Q， WANG X， LIU S B， et al. The alkaline stability and fuel cell performance of poly （N⁃spirocyclic quaternary ammonium） ionenes as anion exchange membrane［J］. Journal of Membrane Science， 2021， 630： 119325.
4	LI X F， ZHANG B， GUO J， et al. High⁃strength， ultra⁃thin anion exchange membranes with a branched structure toward alkaline membrane fuel cells［J］. Journal of Materials Chemistry A， 2023， 11（20）： 10738⁃10747.
5	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］. Journal of Materials Chemistry A， 2021， 9（1）： 327⁃337.
6	DING Y， LIU C X， MA Y C， et al. Correlation between the humidity⁃dependent surface microstructure and macroconductivity of anion exchange membranes［J］. ACS Applied Materials & Interfaces， 2023， 15（25）： 31057⁃31066.
7	ZHAO J L， GAO J， YANG J Y， et al. Hydrophobic thiophene unit modification for the construction of novel anion exchange membranes for high⁃speed transport of ion channels［J］. ACS Sustainable Chemistry & Engineering， 2024， 12（32）： 12126⁃12134.
8	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］. Advanced Functional Materials， 2023， 33（35）： 2302364.
9	YUAN W， ZENG L P， ZHANG T C， et al. High performance anion exchange membranes with confined sub‐2‐nm ion channel［J］. Advanced Functional Materials， 2023， 33（36）： 2307041.
10	LEE W H， KIM Y S， BAE C. Robust hydroxide ion conducting poly（biphenyl alkylene）s for alkaline fuel cell membranes［J］. ACS Macro Lett， 2015， 4（8）： 814⁃818.
11	LI L J， ZHANG J J， JIANG T， et al. High ion conductivity and diffusivity in the anion exchange membrane enabled by tethering with multication strings on the poly （biphenyl alkylene） backbone［J］. ACS Applied Energy Materials， 2020， 3（7）： 6268⁃6279.
12	WAN X F， WEI X T， GE J M， et al. Towards highly conducting and stable poly（fluorenyl biphenyl）⁃based anion exchange membranes by grafting dual Y⁃shaped side⁃chains［J］. Journal of Membrane Science， 2023， 680： 121760.
13	XU F， CHEN Y B， CAO X T， et al. Comb⁃shaped polyfluorene with variable alkyl chain length for application as anion exchange membranes［J］. Journal of Power Sources， 2022， 545： 231880.
14	LIU Y J， GAO W T， ZHU A M， et al. High⁃performance di⁃piperidinium⁃crosslinked poly（p⁃terphenyl piperidinium） anion exchange membranes［J］. Journal of Membrane Science， 2023， 687： 122045.
15	ZHAO Z X， YANG Z J， ZHANG M H， et al. Tripartite cationic interpenetrating polymer network anion exchange membranes for fuel cells［J］. ACS Applied Energy Materials， 2023， 6（3）： 1488⁃1500.
16	CHENG X， LI C H， ZOU X W， et al. Multi⁃cation alkoxy chains with high ion conductivity and durability in cross⁃linked poly （aryl piperidinium） anion exchange membranes［J］. Separation and Purification Technology， 2024， 345： 127418.
17	WANG X Q， FANG Z Y， ZHANG M， et al. Macromolecular crosslinked poly（aryl piperidinium）⁃based anion exchange membranes with enhanced ion conduction for water electrolysis［J］. Journal of Membrane Science， 2024， 700： 122717.
18	MA L L， HUSSAIN M， LI L， et al. Octopus⁃like side chain grafted poly（arylene piperidinium） membranes for fuel cell application［J］. Journal of Membrane Science， 2021， 636： 119529.
19	WANG X Q， LAMMERTINK R G H. Dimensionally stable multication⁃crosslinked poly（arylene piperidinium） membranes for water electrolysis［J］. Journal of Materials Chemistry A， 2022， 10（15）： 8401⁃8412.
20	GAO W T， GAO X L， GOU W W， et al. High⁃performance tetracyclic aromatic anion exchange membranes containing twisted binaphthyl for fuel cells［J］. Journal of Membrane Science， 2022， 655： 120578.
21	XIE N， WANG T， DU S H， et al. High⁃performance and stable poly（carbazole）⁃based anion exchange membrane containing rigid⁃flexible coupled side⁃chains for fuel cells［J］. Journal of Power Sources， 2023， 574： 233121.

[1]	Weimin GAO, Jilin WANG, Quantong CHE. Research Progress of Flexible Proton Exchange Membranes [J]. Journal of Liaoning Petrochemical University, 2024, 44(6): 32-41.
[2]	Yanan WANG, Chuchu MENG, Liran PEI, Xitong WANG, Junhua LI, Jianhua QIAN. Preparation of the Reduced Graphene Oxide⁃Based Tin Selenide Nano⁃Petal Composite and Its Electrocatalytic Properties [J]. Journal of Liaoning Petrochemical University, 2024, 44(6): 42-50.
[3]	Jing LU, Lulu WANG, Hui GAO, Jilin WANG. Preparation and Characterization of Semi⁃Interpenetrating Network Anion Exchange Membranes for Fuel Cells [J]. Journal of Liaoning Petrochemical University, 2024, 44(6): 51-58.
[4]	Jing JIANG, Yunfeng SONG, Ji MA, Lei ZHANG, Leilei ZHANG, Zhaoyuan SONG. Electrochemical Properties of Co⁃Doped La_1.5Ca_0.5NiO₄₊_δ Cathode Materials [J]. Journal of Liaoning Petrochemical University, 2024, 44(2): 29-35.
[5]	Xiaogang SU, Zhaoyuan SONG, Leilei ZHANG. Investigation on Ba₂Fe_1.3Mo_0.7O_6-_δ Double Perovskite as Anode Material for Solid Oxide Fuel Cell [J]. Journal of Liaoning Petrochemical University, 2024, 44(1): 29-34.
[6]	Yufu Yang, Jiangxin Li, Pengcheng Wang, Yuankui Teng, Fangjun Jin. Progress of Molybdate⁃Based Perovskites as Anode Materials for Solid Oxide Fuel Cells [J]. Journal of Liaoning Petrochemical University, 2023, 43(1): 21-26.
[7]	Yao Guibin，Cai Hongdong，Zhang Leilei，Xu Jingsheng，Song Zhaoyuan. Electrochemical Performance of A⁃Deficiency Double Perovskite Sr1.85MgMoO6-δ Anode [J]. Journal of Liaoning Petrochemical University, 2019, 39(4): 28-33.
[8]	Zhang Leilei, Li Chuang, Song Zhaoyuan, Long Wen, Zhang Lei. Review of SOFC Anode with Resistance to Carbon Deposition [J]. Journal of Liaoning Petrochemical University, 2015, 35(6): 6-11,19.
[9]	Zhang Leilei, Chang Ying, Huang Jinhua, Song Zhaoyuan, Fu Yidan, Liu Mo. Investigation of BSCN0.630%GDC Composite Cathode for ITSOFC [J]. Journal of Liaoning Petrochemical University, 2014, 34(2): 4-8.
[10]	ZHANG Leilei, LI Zhou, CHEN Mingming, HE Tianmin. reparation and Characterization of Perovskite Oxide Ba0.6Sr0.4Co0.9Nb0.1O3δ as a Novel Cathode Material for ITSOFCs [J]. Journal of Liaoning Petrochemical University, 2013, 33(2): 6-10.
[11]	HUANG Jing-feng， LIU Feng， TANG Jun. Electrochemical Properties of High Nitrogen Stainless Steel Under Simulated PEM Fuel Cell Environment [J]. Journal of Liaoning Petrochemical University, 2011, 31(4): 56-59.