Study on the Polyamine Thin Film Composite Membrane for Vanadium Battery

doi:10.6023/A23080375

Abstract

Vanadium redox flow battery (VRB) exhibits the advantages of independent capacity and power, easy modularization, long lifespan and high safety, which make it particularly suitable for use in large-scale energy storage systems. The separator is one of the key components of VRB, which has a significant impact on the overall performance and cost of the battery. Perfluorosulfonic acid membranes such as Nafion (DuPont) possesses the advantages of high chemical stability, high conductivity and good mechanical properties, therefore it has been widely used as commercial membrane in VRB. However, Nafion has the two main drawbacks of high vanadium ion permeability and high cost when used in VRB, which seriously restricts the commercialization process of VRB. Thin film composite (TFC) membranes have the advantages of easy regulation of the skin layer and substrate layer, simple preparation process and high ion selectivity, which make them particularly suitable for VRB system. However, traditional polyamide TFC membranes have potential problems of hydrolysis and decomposition in VRB strong acid electrolytes. In order to obtain a high stable TFC membrane for VRB application, polyethylenimine (PEI) and cyanuric chloride (CC) were used as monomers to prepare polyamine TFC membrane via interfacial polymerization (IP) method. Detailed physico-chemical and electrochemical performances of the membranes including vanadium permeability, single cell charge-discharge performances, chemical stability and long-term charge-discharge have been measured. The results showed that the vanadium permeability of M_T is 3.17×10^-7 cm²•min^-1, which is dramatically lower than that of M₀ (30.89×10^-7 cm²•min^-1) and commercial N 115 (Nafion 115, 10.91×10^-7 cm²•min^-1) membranes. The energy efficiency (EE) of M_T membrane at 40 mA•cm^-2 reached up to 86.2%, which was much higher than that of M₀ (74.9%) and N 115 (80.0%) membranes. Chemical stability test proved that the permeability loss rate of M_T was 4.42%, which is smaller than that of M₀ (8.93%) and N 115 (4.86%). At the current density of 80 mA•cm^-2, the prepared TFC membrane has shown stable coulombic efficiency, voltage efficiency and energy efficiency. The TFC membrane is the ideal substitutes for commercial Nafion membrane and has great promise of application in VRB.

Key words: vanadium battery, polyamine, thin film composite membrane, interfacial polymerization, porous membrane

Cite this article

Xiangguo Teng, Liangwei Zhang, Xiaoyu Han, Guowei Li, Jicui Dai. Study on the Polyamine Thin Film Composite Membrane for Vanadium Battery[J]. Acta Chimica Sinica, 2024, 82(1): 16-25.

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Fig. & Tab. 16

Figure 1. Illustration of the mechanism of substrate and polyamine TFC membranes in VRB application

Figure 2. SEM images of M0 and MT membranes: (a) surface image of M0 (100×); (b) surface image of MT (100×); (c) surface image of M0 (1000×); (d) surface image of MT (1000×); (e) cross sectional image of M0 (500×); (f) cross sectional image of MT (500×)

Figure 3. ATR-FTIR spectra of the M0 and MT

Figure 4. XPS spectra of the M0 and MT

Figure 5. Comparison of WU and SR of the M0, MT and N 115 membranes

Figure 6. Comparison of stress-strain curves of MT and N 115 membranes under dry and wet condition

Figure 7. (a) Vanadium ion permeability curves of the M0, MT and N 115; (b) vanadium ion permeability coefficients of the M0, MT and N 115

Figure 8. (a) Proton permeability curves of the M0, MT and N 115; (b) ion selectivity of the M0, MT and N 115

膜	质量损失率/%	浸泡前钒离子渗透系数/ (×10^-7 cm²•min^-1)	浸泡后钒离子渗透系数/ (×10^-7 cm²•min^-1)	钒离子渗透系数损失率/%
M₀	2.85	30.89	33.65	8.93
M_T	1.66	3.17	3.31	4.42
N 115	1.73	10.91	11.44	4.86

Table 1. Results of chemical stability data of the MT和N 115 membranes before and after soaking

Figure 9. Comparison of area resistance (a) and conductivity (b) of the M0, MT and N 115 membranes

Figure 10. Variation of (a) CE, (b) VE and (c) EE with current density of the M0, MT and N 115 membranes at 40~80 mA?cm-2

膜	电流密度/ (mA•cm^-2)	CE/%	VE/%	EE/%	文献
全氟磺酸填充多孔聚乙烯	60	≈93	≈85	≈79	[51]
三维聚偏氟乙烯多孔膜	100	96	85	82	[19]
聚苯并咪唑/聚乙烯吡咯烷酮	100	99.26	74.15	74.79	[52]
磺化聚酰亚胺/聚乙烯吡咯烷酮	20	95	71	67.5	[49]
Nafion填充多孔聚偏氟乙烯膜	80	≈93	≈73	≈68	[53]
二维MFI 分子筛膜	80	97.5	77.2	75.2	[54]
聚酰胺薄层复合膜	80	99.2	92.8	92.1	[34]
多巴胺改性的聚酰胺薄层复合膜	80	95.7	86.8	83.1	[48]
层层自组装改性聚醚砜多孔膜	80	98	89.8	88	[27]
聚胺薄层复合膜	80	97.9	79.8	78.1	本文

Table 2. Comparison of CE, VE and EE of the as prepared membrane with partial reported literature

Figure 11. (a) Self-discharge curves of the M0, MT and N 115 membranes and (b) long cycling performance of MT membrane

Figure 12. (a) FTIR spectra of MT membrane before and after long cycling, (b) SEM image of MT after long cycling, (c) EDS mapping of N element corresponding to (b)

Figure 13. 1H NMR spectra of SPEEK

Figure 14. Reaction equation for preparing polyamine by interfacial polymerization

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钒电池用聚胺薄层复合膜研究