钒电池用聚胺薄层复合膜研究

doi:10.6023/A23080375

摘要/Abstract

钒电池(VRB)具有容量和功率相互独立、易于模块化、寿命长和安全性高等优点, 因此特别适合作为大规模储能系统使用. 隔膜是VRB的核心部件之一, 对电池的综合性能和成本影响巨大. 全氟磺酸膜如Nafion(杜邦)具有化学稳定性高、电导率高和机械性能好等优点, 因此是当前VRB中所广泛使用的商业化隔膜. 然而, Nafion用于VRB时存在着钒离子渗透率高和成本高两大主要缺点, 严重制约了VRB的商业化进程. 薄层复合(TFC)膜具有皮层和支撑层易调控、制备简单和离子选择性高等特点, 特别适合于在VRB中使用. 但是传统的聚酰胺型TFC膜在VRB强酸电解液中存在潜在的水解和分解问题. 为了制备VRB用高稳定性TFC膜, 本工作以聚乙烯亚胺(PEI)和三聚氰氯(CC)作为两相单体, 通过界面聚合法制备了不含酰胺基的聚胺型TFC膜并应用于VRB. 在此基础上, 对所制备复合膜进行了钒离子渗透率、单电池充放电性能、化学稳定性和长期循环稳定性等物化性能及电化学性能研究. 结果表明: 聚胺TFC膜(M_T)的钒离子渗透系数为3.17×10^-7 cm²•min^-1, 远小于基膜M₀ (30.89×10^-7 cm²•min^-1)和商业N 115膜(Nafion 115, 10.91×10^-7 cm²•min^-1). M_T膜在40 mA•cm^-2的电流密度下的能量效率(EE)高达86.2%, 远高于M₀ (74.9%)和N 115 (80.0%)膜. 化学稳定性测试表明M_T膜的钒离子渗透系数损失率为4.42%, 低于M₀ (8.93%)和N 115 (4.86%). 在80 mA•cm^-2的电流密度下100次充放电循环内, 所制备TFC膜具有稳定的库仑效率、电压效率和能量效率. 该TFC膜是理想的商业Nafion膜替代产品, 在VRB中有良好的应用前景.

关键词: 钒电池, 聚胺, 薄层复合膜, 界面聚合, 多孔膜

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

引用此文

滕祥国, 张良伟, 韩晓玉, 李郭威, 戴纪翠. 钒电池用聚胺薄层复合膜研究[J]. 化学学报, 2024, 82(1): 16-25.

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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图/表 16

图1. 多孔基膜和聚胺TFC膜用于VRB的示意图

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

图2. M0和MT膜的SEM图: (a) M0表面图(100×); (b) MT表面图 (100×); (c) M0表面图(1000×); (d) MT表面图(1000×); (e) M0断面图(500×); (f) MT断面图(500×)

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×)

图3. M0和MT的ATR-FTIR谱图

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

图4. M0和MT的XPS谱图

Figure 4. XPS spectra of the M0 and MT

图5. M0、MT和N 115膜的含水率(WU)及溶胀率(SR)对比

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

图6. MT和N 115膜干湿状态下应力-应变曲线对比

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

图7. (a) M0、MT和N 115膜的钒离子渗透曲线; (b) M0、MT和N 115膜的钒离子渗透系数

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

图8. (a) M0、MT和N 115膜的氢离子渗透曲线; (b) M0、MT和N 115膜的离子选择性对比

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

表1. MT和N 115膜浸泡前后化学稳定性结果

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

图9. M0、MT和N 115膜的面电阻(a)和电导率(b)比较

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

图10. 40~80 mA?cm-2电流密度下M0、MT和N 115膜的(a) CE, (b) VE和(c) EE随电流密度变化关系图

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

表2. 本文所制备复合膜的CE、VE和EE与部分文献结果对比

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

图11. (a) M0、MT和N 115膜的自放电曲线和(b) MT膜的长循环性能

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

图12. (a) MT膜长循环前后傅立叶变换红外光谱, (b)长循环后MT膜的SEM图, (c)相应于图(b)的N元素能谱分布图

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)

图13. SPEEK的1H NMR图

Figure 13. 1H NMR spectra of SPEEK

图14. 界面聚合反应制备聚胺TFC膜反应方程式

Figure 14. Reaction equation for preparing polyamine by interfacial polymerization

参考文献 68

[1]	Cunha, Á.; Martins, J.; Rodrigues, N.; Brito, F. P. Int. J. Energ. Res. 2015, 39, 889. doi: 10.1002/er.v39.7
[2]	Ding, C.; Zhang, H.; Li, X.; Liu, T.; Xing, F. J. Phys. Chem. Lett. 2013, 4, 1281. doi: 10.1021/jz4001032
[3]	Yang, Z.; Zhang, J.; Kintner-Meyer, M. C. W.; Lu, X.; Choi, D.; Lemmon, J. P.; Liu, J. Chem. Rev. 2011, 111, 3577. doi: 10.1021/cr100290v
[4]	Soloveichik, G. L. Chem. Rev. 2015, 115, 11533. doi: 10.1021/cr500720t pmid: 26389560
[5]	Kear, G.; Shah, A. A.; Walsh, F. C. Int. J. Energ. Res. 2012, 36, 1105. doi: 10.1002/er.v36.11
[6]	Zhang, H.-M.; Wang, X.-L.; 2013, 2, 281. (in Chinese)
	(张华民, 王晓丽, 储能科学与技术, 2013, 2, 281.) doi: 10.3969/j.issn.2095-4239.2013.03.014
[7]	Skyllas-Kazacos, M.; Rychcik, M.; Robins, R. G.; Fane, A. G.; Green, M. A. J. Electrochem. Soc. 1986, 133, 1057. doi: 10.1149/1.2108706
[8]	Rychcik, M.; Skyllas-Kazacos, M. J. Power Sources 1988, 22, 59. doi: 10.1016/0378-7753(88)80005-3
[9]	Jia, Z.-J.; Song, S.-Q.; Wang, B.-G. 2012, 1, 50. (in Chinese)
	(贾志军, 宋士强, 王保国, 储能科学与技术, 2012, 1, 50.)
[10]	Liu, M.-Y.; Han, L.-W.; Zheng, J.-T.; Xu, H.-W.; Cao, C.-Z. Chinese Journal of Power Sources 2016, 40, 1330. (in Chinese)
	(刘明义, 韩临武, 郑建涛, 徐海卫, 曹传钊, 电源技术, 2016, 40, 1330.)
[11]	Doan, T. N. L.; Hoang, T. K. A.; Chen, P. RSC Adv 2015, 5, 72805. doi: 10.1039/C5RA05914C
[12]	Zhang, B.-G.; Zhang, S.-H.; Xing, D.-B.; Yin, C.-X.; Han, R.-L.; Jian, X.-G. 2011, 69, 583. (in Chinese)
	(张本贵, 张守海, 邢东博, 尹春香, 韩润林, 蹇锡高, 化学学报, 2011, 69, 583.)
[13]	Prifti, H.; Parasuraman, A.; Winardi, S.; Lim, T. M.; Skyllas-Kazacos, M. Membranes-Basel 2012, 2, 275.
[14]	Shi, Y.; Eze, C.; Xiong, B.; He, W.; Zhang, H.; Lim, T. M.; Ukil, A.; Zhao, J. Appl. Energ. 2019, 238, 202. doi: 10.1016/j.apenergy.2018.12.087
[15]	Schwenzer, B.; Zhang, J.; Kim, S.; Li, L.; Liu, J.; Yang, Z. ChemSusChem 2011, 4, 1388. pmid: 22102992
[16]	Ding, Y.; Wang, L.-H.; Han, X.-T.; 2013, 1476. (in Chinese)
	(丁跃, 王丽华, 韩旭彤, 高分子学报, 2013, 1476.)
[17]	Li, X.; Zhang, H.; Mai, Z.; Zhang, H.; Vankelecom, I. Energ. Environ. Sci. 2011, 4, 1147. doi: 10.1039/c0ee00770f
[18]	Fetyan, A.; Benetho, B. P.; Bamgbopa, M. O. J. Energy Chem. 2023, 81, 64. doi: 10.1016/j.jechem.2023.01.058
[19]	Wang, F.-R.; Jiang, F.-J. Acta Chim. Sinica 2021, 79, 1123. (in Chinese) doi: 10.6023/A21050231
	(王斐然, 蒋峰景, 化学学报, 2021, 79, 1123.) doi: 10.6023/A21050231
[20]	Ahn, Y.; Kim, D. Energy Storage Mater. 2020, 31, 105.
[21]	Wang, F.-R.; Jiang, F.-J. Prog. Chem. 2021, 33, 462. (in Chinese)
	(王斐然, 蒋峰景, 化学进展, 2021, 33, 462.) doi: 10.7536/PC200567
[22]	Zhang, S.; Liu, Q.-H.; John, L.; Miao, P.; Jiang, Z. Y.; 2020, 40, 50. (in Chinese)
	(张赛, 刘庆华, John, L. 缪平, 姜忠义, 现代化工, 2020, 40, 50.)
[23]	Zhang, H.; Zhang, H.; Li, X.; Mai, Z.; Zhang, J. Energ. Environ. Sci. 2011, 4, 1676. doi: 10.1039/c1ee01117k
[24]	Zhou, X.; Xue, R.; Zhong, Y.; Zhang, Y.; Jiang, F. J. Membrane Sci. 2020, 595, 117614. doi: 10.1016/j.memsci.2019.117614
[25]	Lu, W.; Yuan, Z.; Zhao, Y.; Qiao, L.; Zhang, H.; Li, X. Energy Storage Mater. 2018, 10, 40.
[26]	Mögelin, H.; Yao, G.; Zhong, H.; Dos Santos, A. R.; Barascu, A.; Meyer, R.; Krenkel, S.; Wassersleben, S.; Hickmann, T.; Enke, D.; Turek, T.; Kunz, U. J. Power Sources 2018, 377, 18. doi: 10.1016/j.jpowsour.2017.12.001
[27]	Zhao, Y.; Yuan, Z.; Lu, W.; Li, X.; Zhang, H. J. Power Sources 2017, 342, 327. doi: 10.1016/j.jpowsour.2016.12.058
[28]	Chae, I. S.; Luo, T.; Moon, G. H.; Ogieglo, W.; Kang, Y. S.; Wessling, M. Adv. Energy Mater. 2016, 6, 1600517. doi: 10.1002/aenm.v6.16
[29]	Lu, W.; Yuan, Z.; Zhao, Y.; Zhang, H.; Zhang, H.; Li, X. Chem. Soc. Rev. 2017, 46, 2199. doi: 10.1039/C6CS00823B
[30]	Wu, J.; Dai, Q.; Zhang, H.; Li, X. ChemSusChem 2020, 13, 3805. doi: 10.1002/cssc.v13.15
[31]	Xu, Z.; Huang, K. Chem. Ind. Eng. Prog. 2022, 41, 1569. (in Chinese)
	(徐至, 黄康, 化工进展, 2022, 41, 1569.) doi: 10.16085/j.issn.1000-6613.2021-2213
[32]	Zhang, H.-J.; Shen, J.-N.; Gao, C.-J.; 2017, 27, 6. (in Chinese)
	(张慧娟, 沈江南, 高从堦, 过滤与分离, 2017, 27, 6.)
[33]	Xu, G.; Wang, J.; Li, C. Desalination 2013, 328, 83. doi: 10.1016/j.desal.2013.08.022
[34]	Dai, Q.; Liu, Z.; Huang, L.; Wang, C.; Zhao, Y.; Fu, Q.; Zheng, A.; Zhang, H.; Li, X. Nat. Commun. 2020, 11, 13. doi: 10.1038/s41467-019-13704-2
[35]	Liang, S.; Xu, G.; Jin, Y.; Wu, Z.; Cai, Z.; Zhao, N.; Wu, Z. J. Membrane Sci. 2015, 476, 475. doi: 10.1016/j.memsci.2014.12.003
[36]	Yao, C. W.; Burford, R. P.; Fane, A. G.; Fell, C. J. D.; Mcdonogh, R. M. J. Appl. Polym. Sci. 1987, 34, 2399. doi: 10.1002/app.1987.070340706
[37]	Dalwani, M.; Benes, N. E.; Bargeman, G.; Stamatialis, D.; Wessling, M. J. Membrane Sci. 2011, 372, 228. doi: 10.1016/j.memsci.2011.02.012
[38]	Lee, K. P.; Zheng, J.; Bargeman, G.; Kemperman, A. J. B.; Benes, N. E. J. Membrane Sci. 2015, 478, 75. doi: 10.1016/j.memsci.2014.12.045
[39]	Ma, X.; Wen, X.; Gu, S.; Xu, Z.; Zhang, J. J. Membrane Sci. 2013, 430, 62. doi: 10.1016/j.memsci.2012.11.073
[40]	Lu, W.; Yuan, Z.; Li, M.; Li, X.; Zhang, H.; Vankelecom, I. Adv. Funct. Mater. 2017, 27, 1604587. doi: 10.1002/adfm.v27.4
[41]	Lau, W.; Ismail, A. F. Desalination 2009, 249, 996. doi: 10.1016/j.desal.2009.09.016
[42]	Jaafar, J.; Ismail, A. F.; Mustafa, A. Mat. Sci. Eng. A.-Struct. 2007, 460, 475.
[43]	Daud, S. N. S. S.; Norddin, M. N. A. M.; Jaafar, J.; Sudirman, R.; Othman, M. H. D.; Ismail, A. F. Arab. J. Sci. Eng. 2021, 46, 6189. doi: 10.1007/s13369-020-04898-5
[44]	Lau, W. J.; Ismail, A. F. J. Membrane Sci. 2009, 334, 30. doi: 10.1016/j.memsci.2009.02.012
[45]	Bai, L.; Wang, M.; Li, Z.; Yang, H.; Peng, Z.; Zhao, Y. J. Membrane Sci. 2022, 643, 120012. doi: 10.1016/j.memsci.2021.120012
[46]	Jiang, Z.; Miao, J.; He, Y.; Hong, X.; Tu, K.; Wang, X.; Chen, S.; Yang, H.; Zhang, L.; Zhang, R. RSC Adv. 2019, 9, 37546. doi: 10.1039/C9RA06528H
[47]	Zhu, X.; Cheng, X.; Luo, X.; Liu, Y.; Xu, D.; Tang, X.; Gan, Z.; Yang, L.; Li, G.; Liang, H. Environ. Sci. Technol. 2020, 54, 6365. doi: 10.1021/acs.est.9b06779
[48]	Teng, X.; Guo, Y.; Liu, D.; Li, G.; Yu, C.; Dai, J. J. Membrane Sci. 2020, 601, 117906. doi: 10.1016/j.memsci.2020.117906
[49]	Zhang, B.; Liu, S.; Wang, L. H.; Han, X. T.; 2015, 418. (in Chinese)
	(张斌, 刘帅, 王丽华, 韩旭彤, 高分子学报, 2015, 418.)
[50]	Tian, J.; Chang, H.; Gao, S.; Zhang, R. Desalination 2020, 491, 114499. doi: 10.1016/j.desal.2020.114499
[51]	Thong, P. T.; Ajeya, K. V.; Dhanabalan, K.; Roh, S.; Son, W.; Park, S.; Jung, H. J. Power Sources 2022, 521, 230912. doi: 10.1016/j.jpowsour.2021.230912
[52]	Song, X.-P.; Liu, J.-Y.; Wang, L.-H.; Han, X.-T.; Huang, Q.-L. 2019, 40, 1543. (in Chinese)
	(宋西鹏, 刘金宇, 王丽华, 韩旭彤, 黄庆林, 高等学校化学学报, 2019, 40, 1543.) doi: 10.7503/cjcu20180720
[53]	Dalal, U.; Kapoor, M.; Verma, A. Energ. Fuel. 2023, 37, 13457. doi: 10.1021/acs.energyfuels.3c01932
[54]	Zhang, D.; Huang, K.; Xia, Y.; Cao, H.; Dai, L.; Qu, K.; Xiao, L.; Fan, Y.; Xu, Z. Angew. Chem. Int. Ed. 2023, 62, e2023109.
[55]	Guo, C.-S. Ph.D. Dissertation, Tiangong University, Tianjin, 2022. (in Chinese)
	(郭昌盛, 博士论文, 天津工业大学,天津, 2022.)
[56]	Shi, Q.; Ni, L.; Zhang, Y.; Feng, X.; Chang, Q.; Meng, J. J. Mater. Chem. A 2017, 5, 13610. doi: 10.1039/C7TA02552A
[57]	Hu, P.; He, J.; Tian, B.; Xu, Z.; Yuan, T.; Sun, H.; Li, P.; Niu, Q. J. Desalination 2020, 496, 114340. doi: 10.1016/j.desal.2020.114340
[58]	Zhu, X.; Tang, X.; Luo, X.; Yang, Z.; Cheng, X.; Gan, Z.; Xu, D.; Li, G.; Liang, H. J. Membrane Sci. 2021, 618, 118738. doi: 10.1016/j.memsci.2020.118738
[59]	Zeng, H.; Li, Y.; Wang, C. Sep. Purif. Technol. 2020, 236, 116258. doi: 10.1016/j.seppur.2019.116258
[60]	Aravind, K.; Sangeetha, D. Int. J. Polym. Mater. Polym. Biomat. 2014, 64, 220. doi: 10.1080/00914037.2014.936594
[61]	Zhang, R.; Yu, S.; Shi, W.; Zhu, J.; Van der Bruggen, B. Sep. Purif. Technol. 2019, 215, 670. doi: 10.1016/j.seppur.2019.01.045
[62]	Li, G.-W. M.S. Thesis, Harbin Institute of Technology, Haerbin, 2019. (in Chinese)
	(李郭威, 硕士论文, 哈尔滨工业大学,哈尔滨, 2019.)
[63]	Hasbullah, N.; Sekak, K. A.; Ibrahim, I.; Mahmood, M. R.; Soga, T.; Nagaoka, S.; Mamat, M. H.; Jafar, S. M. Aip Conference Proceedings 2016, 1733, 020049.
[64]	Dong, Y.-F.; Tan, X.-L.; Guo, Q.; Li, X.; Li, D.; Li, M. Physical Testing and Chemical Analysis Part A: Physical Testing 2011, 47, 535 (in Chinese)
	(董云凤, 谭孝林, 郭强, 李夏, 李丹, 李萌, 理化检验(物理分册), 2011, 47, 535.)
[65]	Yuan, Z.; Zhu, X.; Li, M.; Lu, W.; Li, X.; Zhang, H. Angew. Chem. Int. Ed. 2016, 55, 3058. doi: 10.1002/anie.v55.9
[66]	Zheng, L.; Wang, H.; Niu, R.; Zhang, Y.; Shi, H. Electrochim. Acta 2018, 282, 437. doi: 10.1016/j.electacta.2018.06.083
[67]	Wang, N.-F. Ph.D. Dissertation, Central South University, Changsha, 2012. (in Chinese)
	(汪南方, 博士论文, 中南大学, 长沙, 2012.)
[68]	Wang, F.; Zhang, Z.; Jiang, F. J. Power Sources 2021, 506, 230234. doi: 10.1016/j.jpowsour.2021.230234