發(fā)布時間：2018-04-19 19:50

  本文選題：全釩液流電池 + 質子交換膜��； 參考：《深圳大學》2015年碩士論文

【摘要】：在大力發(fā)展可再生能源的背景下,儲能技術也在飛速發(fā)展。全釩液流電池作為一種具有潛力的儲能系統(tǒng),具有低成本、長壽命、可深度充放電和設計靈活等特點,在太陽能和風力發(fā)電的儲能設備、后備電源、電網的削峰填谷等方面有望得到應用。作為全釩液流電池重要的部件之一,質子交換膜直接影響著電池的成本、性能和壽命。目前廣泛使用的質子交換膜為全氟結構的Nafion膜,但由于其價格昂貴、釩離子滲透率高,制約了全釩液流電池的發(fā)展。因而尋找價格合適、離子選擇性高且壽命較長的非氟離子膜就成為研究的熱點。本論文以低成本的非氟型磺化聚芳醚酮和磺化聚醚醚酮為研究對象,進行合理設計或改性,制備出幾種特別適用于全釩液流電池的高選擇性離子膜,并提出了可能的作用機制。通過雙酚芴、磺化二氟酮鈉、二氟二苯砜和具有剛性苯環(huán)結構的B3單體的縮聚反應合成了支化度為8%的聚芳醚酮聚合物(HSPAEK)。HSPAEK具有良好的溶解性,HSPAEK膜透明、具有柔韌性。SEM和EDX圖顯示其表面和斷面都是致密均勻的。HSPAEK膜具有低溶脹率、適中的吸水率和質子電導率。除此之外,HSPAEK膜還具有很低的VO~(2+)滲透率,因而具有較好的離子選擇性和較長的自放電時間。裝入全釩液流電池中,HSPAEK膜具有較高的庫侖效率和容量保持率,說明HSPAEK膜具有較好的化學穩(wěn)定性,因而在全釩液流電池中具有一定應用潛力。通過在SPEEK膜內摻雜三種納米無機氧化物(Al_2O_3、SiO_2和TiO_2)制備了SPEEK基復合膜,考察了納米無機氧化物的質量分數(2.5%、5%、7.5%、10%)對復合膜的結構與性能的影響。通過SEM觀察發(fā)現,復合膜體相致密且摻雜物分布較為均勻。無機納米氧化物(Al_2O_3、SiO_2和TiO_2)的質量摻雜比例為5%的三種膜(S/A-5%、S/S-5%、S/T-5%)性能最好。S/A-5%、S/S-5%、S/T-5%膜相比于純SPEEK膜,具有更好的熱穩(wěn)定性、機械強度和化學穩(wěn)定性。與Nafion 117和純SPEEK膜相比,復合膜具有較低的VO~(2+)滲透率。由于S/A-5%、S/S-5%、S/T-5%具有較高的離子選擇性(低VO~(2+)滲透率與適中的質子電導率),與Nafion117和純SPEEK膜相比,復合膜具有較高的能量效率。在200圈的循環(huán)壽命測試后,S/A-5%的容量保持率為53.3%,S/S-5%為50.8%,S/T-5%為39.5%,都高于Nafion 117的24.7%,顯示出復合膜的較高穩(wěn)定性。通過聚多巴胺(PDA)對納米SiO_2進行表面包覆修飾,得到了表面帶氨基的SiO_2納米粒子,通過TEM觀察發(fā)現PDA-SiO_2表面可以看到一層2-3 nm的包覆層。PDA-SiO_2作為填料摻入SPEEK膜中,復合膜的能量效率較SPEEK膜有所提高,但壽命相比于S/S-5%復合膜反而降低了。
[Abstract]:In the context of the development of renewable energy, energy storage technology is also developing rapidly. As a potential energy storage system, all vanadium liquid flow battery has the characteristics of low cost, long life, deep charge and discharge, flexible design, etc., in solar and wind energy storage equipment, backup power, It is expected that the peak cutting and valley filling of power grid will be applied. As one of the important components of vanadium liquid flow battery, proton exchange membrane directly affects the cost, performance and lifetime of the battery. The widely used proton exchange membrane is Nafion membrane with perfluorine structure, but the development of vanadium liquid flow battery is restricted because of its high price and high vanadium ion permeability. Therefore, it has become a hot topic to find non-fluorine ion membranes with high ion selectivity and long lifetime. In this paper, the low cost non fluorinated sulfonated poly (aryl ether ketone) and sulfonated polyether ether ketone (sulfonated polyether ether ketone) were studied, and several kinds of high selective ion membranes were prepared, which are especially suitable for all vanadium liquid flow batteries, and the possible mechanism was put forward. Through the condensation reaction of bisphenol fluorene, sodium difluorone sulfonate, difluorodiphenyl sulfone and B _ 3 monomer with rigid benzene ring structure, the branched polyaryl ether ketone polymer (HSPAEK). HSPAEK has good solubility and transparency. Its surface and section are compact and uniform. HSPAEK film has low swelling rate, moderate water absorption and proton conductivity. In addition, HSPAEK film also has low VO~(2) permeability, so it has better ion selectivity and longer self-discharge time. HSPAEK film has high Coulomb efficiency and capacity retention in vanadium liquid flow battery, which indicates that HSPAEK film has good chemical stability, so it has certain application potential in all vanadium liquid flow battery. SPEEK based composite membranes were prepared by doping Al2O3SiO2 and TiO2 into SPEEK films. The effect of the mass fraction of nano-inorganic oxides on the structure and properties of the composite membranes was investigated. The results of SEM show that the composite films are compact and the dopants are uniformly distributed. The three kinds of films with a mass doping ratio of 5% to 5% of the inorganic nano-oxide Al2O3SiO _ 2 have a better thermal stability, mechanical strength, and chemical stability than the pure SPEEK films. Compared with Nafion 117 and pure SPEEK membranes, the composite membranes have lower VO~(2) permeability. Because of the high ion selectivity (low VO~(2) permeability and moderate proton conductivity, the composite membranes have higher energy efficiency than Nafion117 and pure SPEEK membranes. After 200 cycles of cycle life test, the capacity retention rate of S- / A-5% is 53.3%, and the S- / S-5% is 50.8% and ST-5% is 39.5%, which is higher than that of Nafion 117 (24.7%), which shows the high stability of the composite membrane. SiO_2 nanoparticles with amino groups on the surface of SiO_2 were prepared by surface coating of PDAs. By TEM observation, a 2-3 nm coating layer. PDA-SiO2 was found to be doped into the SPEEK film. The energy efficiency of the composite membrane is higher than that of the SPEEK membrane, but the lifetime of the composite membrane is lower than that of the S / S-5% composite membrane.
【學位授予單位】：深圳大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TM912;TQ425.236

【參考文獻】

相關期刊論文 前4條

1 劉宗光;屈樹新;翁杰;;聚多巴胺在生物材料表面改性中的應用[J];化學進展;2015年Z1期

2 汪南方;劉素琴;;全釩液流電池隔膜的制備與性能[J];化學進展;2013年01期

3 青格樂圖;郭偉男;范永生;王保國;;全釩液流電池用質子傳導膜研究進展[J];化工學報;2013年02期

4 邢丹敏,付永柱,劉富強,劉永浩,衣寶廉,張華民;燃料電池用磺化聚醚醚酮質子交換膜的研究[J];高分子材料科學與工程;2005年03期

，

本文編號：1774477