全钒液流电池用纤维素纳米晶掺杂混合基质膜

doi:10.11949/0438-1157.20241217

摘要/Abstract

摘要：

设计了用于全钒液流电池的纤维素纳米晶（CNC）掺杂的磺化聚醚醚酮（SPEEK）混合基质膜，CNC表面大量的羟基和磺酸基团使其具有良好的亲水性，这些基团的存在也能改善填料和聚合物之间的界面相容性。此外，CNC的高结晶度和高纵横比确保了膜在强酸性和强氧化性条件下高的稳定性以及良好的活性离子阻隔能力。同时其表面丰富的—OH基团与水分子以及SPEEK中丰富的—SO₃H基团构建了高度互连的亲水离子纳米团簇，实现高达0.073 S·cm^-1的质子传导率。使用其组装的电池在120 mA·cm^-2的电流密度下电压效率（VE）可达88.7%，远远超过SPEEK膜（78.3%），表明SPEEK/CNC膜在全钒液流电池中具有良好的应用前景。

关键词: 全钒液流电池, 混合基质膜, 纤维素纳米晶

Abstract:

A cellulose nanocrystal (CNC)-doped sulfonated poly(ether ether ketone) (SPEEK) hybrid matrix membrane was designed for vanadium redox flow batteries. The abundant hydroxyl and sulfonic acid groups on the surface of CNC enhances its hydrophilicity and improves filler-polymer interfacial compatibility. Additionally, the high crystallinity and aspect ratio of CNC provide the membrane with high stability and effective ion barrier properties under harsh acidic and oxidative conditions. The abundant —OH groups on the CNC surface, combined with the —SO₃H groups in SPEEK, created interconnected hydrophilic ion nanoclusters, resulting in excellent proton conductivity of 0.073 S·cm^-1. The assembled battery using this membrane achieves a voltage efficiency (VE) of 88.7% at 120 mA·cm^-2, significantly surpassing that of the SPEEK membrane (78.3%), indicating that SPEEK/CNC membrane has good application prospects in all-vanadium liquid flow batteries.

Key words: vanadium redox flow battery, hybrid matrix membrane, cellulose nanocrystal

中图分类号:

TM 912.9

刘鑫, 郑皓仁, 陈强, 丁静怡, 黄康, 徐至. 全钒液流电池用纤维素纳米晶掺杂混合基质膜[J]. 化工学报, 2025, 76(5): 2294-2303.

Xin LIU, Haoren ZHENG, Qiang CHEN, Jingyi DING, Kang HUANG, Zhi XU. Cellulose nanocrystals-doped hybrid matrix membranes for vanadium flow battery[J]. CIESC Journal, 2025, 76(5): 2294-2303.

图/表 12

图1 SPEEK/CNC混合基质膜： (a) CNC来源；(b) CNC与SPEEK分子式；(c) SPEEK/CNC膜筛分与传质机理

Fig.1 SPEEK/CNC hybrid matrix membrane： (a) source of CNC; (b) molecular formula of CNC and SPEEK; (c) SPEEK/CNC membrane sieving and mass transfer mechanisms

图2 CNC的形貌表征： (a) CNC粉末；(b) CNC粉末的SEM图像；(c) CNC的DMSO分散液；(d) CNC分散液的SEM图像；(e) CNC分散液的TEM图像；(f) CNC分散液的AFM图像

Fig.2 Topography characterization of CNC: (a) powder of CNC; (b) SEM image of CNC powder; (c) DMSO dispersion for CNC; (d) SEM image of CNC dispersion; (e) TEM image of CNC dispersion; (f) AFM image of CNC dispersion

图3 CNC的基本表征： (a) CNC的XPS谱图-S 2p；(b) CNC的Zeta电位图；(c) CNC的水流体力学直径图；(d) CNC的热重图；(e) CNC的XRD谱图；(f) CNC的红外光谱图

Fig.3 Basic characterization of CNC： (a) XPS spectrum of CNC-S 2p; (b) Zeta potential map of CNC; (c) hydrodynamic diameter diagram of CNC; (d) TGA of CNC; (e) XRD spectrum of CNC; (f) FTIR of CNC

图4 SPEEK的核磁共振谱图

Fig.4 NMR spectra of SPEEK

图5 不同CNC掺杂量的SEM图像： (a) SPEEK；(b) S/CNC-1；(c) S/CNC-3；(d) S/CNC-5

Fig.5 SEM images with different CNC doping amounts: (a) SPEEK; (b) S/CNC-1; (c) S/CNC-3; (d) S/CNC-5

图6 不同CNC掺杂量的水接触角图像： (a) SPEEK；(b) S/CNC-1；(c) S/CNC-3；(d) S/CNC-5

Fig.6 Images of water contact angles with varying amounts of CNC doping: (a) SPEEK; (b) S/CNC-1; (c) S/CNC-3; (d) S/CNC-5

图7 不同CNC掺杂量的数据分析： (a)不同CNC掺杂量的XRD谱图；(b)不同CNC掺杂量的热重曲线；(c)不同CNC掺杂量的FTIR谱图

Fig.7 Data analysis of different CNC doping amounts: (a) XRD spectra of different CNC doping amount; (b) TGA curves for different CNC doping levels; (c) FTIR spectra of different CNC doping amounts

图8 不同膜的物理性能测试： (a) 吸水率与溶胀比；(b) 拉伸强度

Fig.8 Evaluation of physical properties of various membrane materials: (a) water absorption and swelling ratio; (b) tensile strength

图9 SPEEK/CNC杂化膜与SPEEK的基础性能： (a) 质子传导率与面积电阻；(b) 钒离子渗透率

Fig.9 Basic properties of SPEEK/CNC hybrid membranes and SPEEK: (a) proton conductivity and area resistance; (b) vanadium ion permeability

图10 不同膜的单电池性能： (a) 库仑效率；(b) 电压效率；(c) 能量效率

Fig.10 Performance of VFB single cells with different membranes: (a) coulombic efficiency; (b) voltage efficiency; (c) energy efficiency

图11 40~120 mA·cm-2下不同膜的电压曲线： (a) SPEEK；(b) S/CNC-3

Fig.11 Voltage curves of different membranes at 40—120 mA·cm-2: (a) SPEEK; (b) S/CNC-3

图12 SPEEK膜与S/CNC-3膜在120 mA·cm-2下的循环稳定性： (a) 120 mA·cm-2下的长循环稳定性；(b) 放电容量保持率

Fig.12 Cycling stability of SPEEK membrane along with S/CNC-3 membrane at 120 mA·cm-2: (a) cycling stability at 120 mA·cm-2; (b) discharge capacity retention

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