本文選題：全釩液流電池 + 質(zhì)子交換膜　； 參考：《深圳大學(xué)》2015年碩士論文

【摘要】：在大力發(fā)展可再生能源的背景下,儲(chǔ)能技術(shù)也在飛速發(fā)展。全釩液流電池作為一種具有潛力的儲(chǔ)能系統(tǒng),具有低成本、長(zhǎng)壽命、可深度充放電和設(shè)計(jì)靈活等特點(diǎn),在太陽(yáng)能和風(fēng)力發(fā)電的儲(chǔ)能設(shè)備、后備電源、電網(wǎng)的削峰填谷等方面有望得到應(yīng)用。作為全釩液流電池重要的部件之一,質(zhì)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(zhì)子交換膜為全氟結(jié)構(gòu)的Nafion膜,但由于其價(jià)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(jià)格合適、離子選擇性高且壽命較長(zhǎng)的非氟離子膜就成為研究的熱點(diǎn)。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(duì)象,進(jìn)行合理設(shè)計(jì)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(jī)制。通過(guò)雙酚芴、磺化二氟酮鈉、二氟二苯砜和具有剛性苯環(huán)結(jié)構(gòu)的B3單體的縮聚反應(yīng)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(zhì)子電導(dǎo)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(zhǎng)的自放電時(shí)間。裝入全釩液流電池中,HSPAEK膜具有較高的庫(kù)侖效率和容量保持率,說(shuō)明HSPAEK膜具有較好的化學(xué)穩(wěn)定性,因而在全釩液流電池中具有一定應(yīng)用潛力。通過(guò)在SPEEK膜內(nèi)摻雜三種納米無(wú)機(jī)氧化物(Al_2O_3、SiO_2和TiO_2)制備了SPEEK基復(fù)合膜,考察了納米無(wú)機(jī)氧化物的質(zhì)量分?jǐn)?shù)(2.5%、5%、7.5%、10%)對(duì)復(fù)合膜的結(jié)構(gòu)與性能的影響。通過(guò)SEM觀察發(fā)現(xiàn),復(fù)合膜體相致密且摻雜物分布較為均勻。無(wú)機(jī)納米氧化物(Al_2O_3、SiO_2和TiO_2)的質(zhì)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(jī)械強(qiáng)度和化學(xué)穩(wěn)定性。與Nafion 117和純SPEEK膜相比,復(fù)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(zhì)子電導(dǎo)率),與Nafion117和純SPEEK膜相比,復(fù)合膜具有較高的能量效率。在200圈的循環(huán)壽命測(cè)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(fù)合膜的較高穩(wěn)定性。通過(guò)聚多巴胺(PDA)對(duì)納米SiO_2進(jìn)行表面包覆修飾,得到了表面帶氨基的SiO_2納米粒子,通過(guò)TEM觀察發(fā)現(xiàn)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(fù)合膜的能量效率較SPEEK膜有所提高,但壽命相比于S/S-5%復(fù)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(xué)位授予單位】：深圳大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TM912;TQ425.236

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