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微波合成Zr-MOF-NH2及Nafion复合质子交换膜的制备与性能

高倩 张柳杰 张辉 徐靖凯 肖伟 李莹

高倩, 张柳杰, 张辉, 等. 微波合成Zr-MOF-NH2及Nafion复合质子交换膜的制备与性能[J]. 复合材料学报, 2024, 42(0): 1-9.
引用本文: 高倩, 张柳杰, 张辉, 等. 微波合成Zr-MOF-NH2及Nafion复合质子交换膜的制备与性能[J]. 复合材料学报, 2024, 42(0): 1-9.
GAO Qian, ZHANG Liujie, ZHANG Hui, et al. Preparation and properties of Zr-MOF-NH2 and doped Nafion composite proton exchange membranes synthesized by microwaves[J]. Acta Materiae Compositae Sinica.
Citation: GAO Qian, ZHANG Liujie, ZHANG Hui, et al. Preparation and properties of Zr-MOF-NH2 and doped Nafion composite proton exchange membranes synthesized by microwaves[J]. Acta Materiae Compositae Sinica.

微波合成Zr-MOF-NH2及Nafion复合质子交换膜的制备与性能

基金项目: 辽宁省自然科学基金(2022-KF-13-05); 辽宁省教育厅面上项目(LJK0411); 抚顺市“抚顺英才计划”项目(FSYC202107010)
详细信息
    通讯作者:

    肖伟,博士,教授,硕士生导师,研究方向为电池隔膜材料、分离纯化用膜材料 E-mail:nuaaxiaowei@163.com

  • 中图分类号: TB332;TQ340.64

Preparation and properties of Zr-MOF-NH2 and doped Nafion composite proton exchange membranes synthesized by microwaves

Funds: Natural Science Foundation of Liaoning Province (2022-KF-13-05); Liaoning Province Education Administration (LJK0411);Fushun Revitalization Talents Program (FSYC202107010)
  • 摘要: 全钒液流电池要求质子交换膜具备优良的离子选择性和理化稳定性。本研究分别采用微波法和传统水热法制备UIO-66-NH2,利用浇筑法制备了UIO-66-NH2/Nafion复合质子交换膜,对膜的理化性质和电池性能进行系统研究。结果表明,UIO-66-NH2在复合膜内形成的氢键网络、酸碱对和自身孔道协同强化了膜的离子选择性。基于微波法(M/N)和传统水热法(T/N)的复合膜综合性能均优于纯树脂膜(P-N)。在掺杂量为3 wt%时,M/N-3膜拉伸强度达到27 MPa,质子传导率和钒离子透过率分别为122.18 mS·cm−1和0.83 × 10−7 cm2·min−1,离子选择性为15.6 × 105 S·min·cm−3,约为P-N膜的30倍,且其电池能量效率达到83.8%-71.7%(100-200 mA·cm−2),优于T/N-3膜(82.7%-71.0%)和P-N膜(79.4%-69.0%)。同时,该电池也显示出更优的循环稳定性和容量保持率。因此,微波法合成的UIO-66-NH2可有效改善质子交换膜的综合性能,在提高钒液流电池性能方面前景较好。

     

  • 图  1  微波合成UIO-66-NH2及Nafion复合膜的制备过程示意图

    Figure  1.  Schematic diagram of the preparation process of Nafion composite membrane

    UIO-66-NH2—representation of MOF when the preparation method does not need to be distinguished; M-U66-NH2 and T-U66-NH2—UIO-66-NH2 prepared by microwave assisted method and traditional hydrothermal method, respectively; M/N-X and T/N-3—composite membranes doped with UIO-66-NH2 prepared by microwave assisted method and traditional hydrothermal method, respectively; P-N—a pure, unmodified Nafion membrane

    图  2  不同温度下微波加热15 min (a-d)、烘箱加热24 h(e)制备UIO-66-NH2的SEM照片及微波加热15 min样品的XRD谱图(f)

    Figure  2.  SEM images of UIO-66-NH2 by microwave heating for 15 min (a-d), oven heating for 24 h (e) and XRD patterns of UIO-66-NH2 by microwave heating (f)

    图  3  膜的表面SEM照片: P-N(a), M/N-1(b),M/N-3(c); 膜的截面SEM照片: P-N (d), M/N-1 (e), M/N-3(f); M/N-3膜的表面EDS分布图(g-j)

    Figure  3.  Surface SEM images of P-N(a), M/N-1(b) and M/N-3(c); cross-section SEM images of P-N(d), M/N-1(e) and M/N-3(f); EDS element images of M/N-3(g-i)

    图  4  M/N-6(a, c)和M/N-9(b, d)膜的截面SEM照片

    Figure  4.  Cross-sectional SEM images of M/N-6(a, c), M/N-9(b, d)

    图  5  M-U66-NH2(a), P-N膜(b)和M/N-3膜(c)的红外光谱图

    Figure  5.  FT-IR spectra of M-U66-NH2 (a), P-N(b) and M/N-3 membranes(c)

    图  6  复合膜的吸水率和溶胀率(a),面电阻和质子传导率(b),力学性能(c)和应力应变曲线(d)

    Figure  6.  Water uptake and swelling ratio(a), area resistance and conductivity(b), mechanical properties(c) and Stress-strain curve of different membranes(d)

    图  7  复合膜的钒离子渗透浓度(a)、钒离子渗透率和离子选择性(b)

    Figure  7.  Vanadium ion permeation concentration(a), Vanadium ion permeability and ion selectivity(b) of composite membranes

    图  8  不同膜所装配电池的CE(a, d),VE(b, e)和EE(c, f)

    Figure  8.  CE (a, d), VE (b, e) and EE (c, f) of VRBs assembled with different membranes

    图  9  150 mA·cm−2电流密度下复合膜所装配电池的循环效率(a),容量保持率(b)和已有报道性能对比(c)

    Figure  9.  Cycle efficiency(a) and capacity retention(b) of composite membranes at 150 mA·cm−2, and reported performance comparison (c)

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出版历程
  • 收稿日期:  2023-11-16
  • 修回日期:  2023-12-22
  • 录用日期:  2023-12-23
  • 网络出版日期:  2024-01-19

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