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1. 天津工业大学材料科学与工程学院,天津,300387
2. 中国科学院化学研究所,北京,100190
纸质出版日期:2015-4-20,
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张斌, 刘帅, 王丽华, 韩旭彤. 磺化聚酰亚胺酸碱复合膜的制备及其在全钒液流电池中的应用[J]. 高分子学报, 2015,(4):418-426.
Bin Zhang, Shuai Liu, Li-hua Wang, Xu-tong Han. Sulfonated Polyimide Acid-Base Blend Membranes for Vanadium Redox Flow Cell Application[J]. Acta Polymerica Sinica, 2015,(4):418-426.
张斌, 刘帅, 王丽华, 韩旭彤. 磺化聚酰亚胺酸碱复合膜的制备及其在全钒液流电池中的应用[J]. 高分子学报, 2015,(4):418-426. DOI: 10.11777/j.issn1000-3304.2015.14310.
Bin Zhang, Shuai Liu, Li-hua Wang, Xu-tong Han. Sulfonated Polyimide Acid-Base Blend Membranes for Vanadium Redox Flow Cell Application[J]. Acta Polymerica Sinica, 2015,(4):418-426. DOI: 10.11777/j.issn1000-3304.2015.14310.
采用高温一步法合成了一系列不同磺化度的三元共聚磺化聚酰亚胺(SPI)
通过控制磺化二胺与非磺化二胺的摩尔比来调节磺化度.选取碱性聚合物聚乙烯吡咯烷酮(PVP)与SPI按质量比1:9进行共混
制成SPI/PVP酸碱复合膜.对复合膜的吸水率、离子交换容量、钒离子渗透率以及电池性能进行了测试.结果表明
随着磺化度的升高
复合膜的吸水率、离子交换容量、质子电导率升高以及钒离子渗透率升高.复合膜的隔膜选择性比Nafion117的选择性好
其中SPI/PVP-3的选择性是Nafion117的10倍.电池性能测试表明
随磺化度的升高
复合膜能量效率升高.其中SPI/PVP-3膜较Nafion117膜具有较高的库伦效率和能量效率
通过循环测试SPI/PVP-3膜性能稳定
充放电理想.
A series of sulfonated polyimides (SPI) which had different degrees of sulfonation were synthesized by high-temperature one-step method with 2
2'-benzidinedisulfonic (BDSA)
oxydiphthalic dianhydride (ODPA) and 4
4'-diaminodiphenyl methane (MDA) monomer.The molar ratio of BDSA and MDA was controlled to get the different SPIs.The SPIs were characterized by Fourier transform infrared spectroscopy
nuclear magnetic resonance analysis and thermogravimetry.The results show that the sulfonated polyimides were successfully synthesized and have good thermal stability with three-step degradation patterns.Then
a series of sulfonated polyimide/polyvinylpyrrolidone (SPI/PVP) acid-base blend membranes were prepared at the mass ratio of 9:1 and applied in vanadium redox flow battery (VRB).SEM images of the membranes show that the phase separation of the blend membrane is more obvious with the increase of the degree of sulfonation.The parameters of the blend membranes were obtained and reported
such as water uptake
ion exchange capacity (IEC)
area resistance and vanadium ion permeability.The blend membranes have lower water uptake and vanadium ion permeability than those of Nafion117.The IEC
water uptake
proton conductivity and the vanadium ion permeability of SPI/PVP acid-base blend membranes increased with increasing the degrees of sulfonation.The selectivity of the membranes is much better than that of Nafion117
Especially SPI/PVP-3
its selectivity is 10 times higher than that of Nafion117 membrane.In the charge-discharge tests the VRB single cell of the SPI/PVP blend membrane shows higher columbic efficiency (CE) and similar energy efficiency (EE) compared with that of Nafion117.And the VE and EE were increased with the increasing of degree of sulfonation
as CE on the contrary.CE and EE of the SPI/PVP-3 membrane are higher than those of Nafion117 membrane.The performance of SPI/PVP-3 in the charge-discharge test of VRB single cell showed good stablilty.All these results demonstrate that the SPI/PVP acid-base blend membrane is a new promising material for VRB application.
磺化聚酰亚胺酸碱复合膜全钒氧化还原液流电池钒离子渗透率电池效率
SPIAcid-base composite membraneVRBVanadium ion permeabilityBattery efficiency
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