全钒液流电池用磺化聚醚醚酮基复合膜的制备与性能

发布时间：2018-01-12 17:33

本文关键词：全钒液流电池用磺化聚醚醚酮基复合膜的制备与性能　出处：《天津工业大学》2017年硕士论文　论文类型：学位论文

【摘要】：全钒氧化还原液流电池(VRB)以其循环寿命长,快速响应时间,深放电能力和低污染排放受到广泛关注。质子交换膜(PEM)是VRB的关键组分,用于离子传导和防止正/负电解质的交叉混合。全氟磺酸(PFSA)质子膜(Nafion系列)具有高的化学、机械稳定性和质子传导率,但高成本和高钒离子渗透性导致VRB的库伦效率和能量效率降低,因而开发新型质子交换膜对VRB商业化有重要意义。以3-氨基苯磺酸为氧化石墨烯(GO)修饰剂,制备了磺酸化氧化石墨烯(SGO),并与磺化聚醚醚酮(SPEEK)共混制备了 SPEEK/SGO复合质子交换膜。结果表明,SGO的加入提高了复合膜的质子传导率。当添加含量3 wt%时,SPEEK/SGO-3的质子传导率为17.6 mS cm-1。单电池测试表明,在30 mA cm-2电流密度下,SPEEK/SGO-3复合膜的库伦效率(CE:95.6%vs90.2%),能量效率(EE:81%vs 73.8%)高于商业化的Nafion 117膜。300次充放电循环表明SPEEK/SGO-3复合膜具有良好的耐氧化刻蚀和机械稳定性。采用多氨基、多纳米孔的类石墨相氮化碳(g-C3N4)二维材料为掺杂剂,制备了 g-C3N4含量不同的SPEEK/g-C3N4复合质子交换膜。结果表明,磺酸根(-S03H)与亚氨基(-NH)、氨基(-NH2)之间的相互作用,降低了钒离子的渗透率。当添加含量为1.5 wt%时,SPEEK/g-C3N4-1.5复合膜的钒离子透过率为 3.73×107 cm2 min-1。在30 30mA cm-2 的电流密度下,SPEEK/g-C3N4-1.5 复合膜的单电池效率为(CE:97%,EE:83.6%),优于商业化Nafion 117(CE:90.2%,EE:73.8%),并且复合膜的能量效率提高10%。300次充放电循环测试表明,SPEEK/g-C3N4质子交换膜展现了在强酸性、强氧化性环境中的结构稳定性和电池效率。
[Abstract]:Due to its long cycle life, rapid response time, deep discharge capacity and low pollution discharge, all vanadium redox liquid flow battery (VRBs) have attracted wide attention. Proton exchange membrane (PEM) is the key component of VRB. For ion conduction and prevention of cross mixing of positive / negative electrolytes. PFSA (perfluorosulfonic acid) proton membrane Nafion series) has high chemical, mechanical stability and proton conductivity. However, the high cost and high vanadium ion permeability lead to the decrease of Coulomb efficiency and energy efficiency of VRB. Therefore, the development of new proton exchange membranes is of great significance to the commercialization of VRB. Using 3-aminobenzenesulfonic acid as the modifier of graphene oxide, the sulfonated graphene oxide (SGOO) was prepared. The SPEEK/SGO composite proton exchange membrane was prepared by blending with sulfonated polyether ether ketone (SPEEK). With the addition of SGO, the proton conductivity of SPEEK / SGO-3 was 17.6 mScm-1.The single cell test showed that the proton conductivity of SPEEK / SGO-3 was 17.6 mScm-1. At the current density of 30 Ma cm-2, the Coulomb efficiency of Speek / SGO-3 composite membrane is 95.6 vs 90.2. Energy efficiency: EE: 81 vs 73.8). Higher than commercial Nafion 117 film. 300 cycles show that SPEEK/SGO-3 composite film has good oxidation resistance and mechanical stability. SPEEK/g-C3N4 composite proton exchange membranes with different content of g-C _ 3N _ 4 were prepared by using multi-nano-pore graphite-like carbon nitride (GN _ 3N _ 4) as dopant. The results show that g-C _ 3N _ 4 composite proton exchange membranes with different contents have been prepared. The interaction between sulfonic acid group (S03H) and iminodium (NHN), amino-aniline (NH2), reduced the permeability of vanadium ion, when the addition content was 1.5 wt%. The vanadium ion transmittance of SPEEK/g-C3N4-1.5 composite membrane is 3.73 脳 10 ~ 7 cm2 min ~ (-1) under the current density of 30 30 Ma cm-2. The efficiency of single cell of SPEEK/g-C3N4-1.5 composite membrane is as follows: CE97 / EEW 83.6, which is superior to commercial Nafion 117C / CE90.2%. The energy efficiency of the composite membrane was increased by 10. 300 charge-discharge cycles. The results showed that the SPEEK / g-C3N4 proton exchange membrane exhibited strong acidity. Structural stability and cell efficiency in strongly oxidized environments.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM912;TB383.2

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