Cellulose nanocrystals-doped hybrid matrix membranes for vanadium flow battery

doi:10.11949/0438-1157.20241217

Abstract

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

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

CLC Number:

TM 912.9

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.

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.

Figures/Tables 12

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

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

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

Fig.4 NMR spectra of SPEEK

Fig.5 SEM images with different CNC doping amounts: (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

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

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

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

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

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

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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