【摘要】：電力設(shè)備是本世紀(jì)人類遇到的最大的挑戰(zhàn)之一。傳統(tǒng)鋰離子電池的非水液態(tài)電解質(zhì)在過(guò)去的二十年有很大的研究進(jìn)展,但是由于液態(tài)電解質(zhì)的固有屬性使得液態(tài)電解質(zhì)存在安全隱患,而且液態(tài)電解質(zhì)的能量密度也無(wú)法滿足實(shí)際應(yīng)用。相比于液態(tài)鋰離子電池,采用聚合物作電解質(zhì)的聚合物鋰離子電池具有更好的實(shí)用性與安全性,從而能夠應(yīng)用于更加廣泛的領(lǐng)域。傳統(tǒng)的固態(tài)聚合物電解質(zhì)是雙離子導(dǎo)體,陰離子與陽(yáng)離子移動(dòng)的造成濃差極化現(xiàn)象使得電池性能均不佳。單離子聚合物電解質(zhì)在保持固態(tài)聚合物電解質(zhì)的優(yōu)點(diǎn)的基礎(chǔ)下避免了雙離子導(dǎo)體的缺陷,但是目前單離子聚合物電解質(zhì)電導(dǎo)率低,不能滿足鋰離子電池的實(shí)際需要。本論文為了提高聚合物電解質(zhì)的電導(dǎo)率,設(shè)計(jì)合成三種固態(tài)單離子聚合物電解質(zhì)薄膜的合成及性能表征。本文首先合成了一系列Li+/EO=1:18的含氟量不同的聚對(duì)苯乙烯磺酸鋰電解質(zhì),通過(guò)核磁共振氫譜,紅外光譜,掃描電鏡,能譜等分析測(cè)試方法對(duì)聚合物電解質(zhì)的結(jié)構(gòu)進(jìn)行了表征,隨后通過(guò)差示掃描量熱分析,熱重分析對(duì)聚合物電解質(zhì)的玻璃化轉(zhuǎn)變溫度和定性進(jìn)行了分析,通過(guò)交流阻抗譜,鋰離子遷移數(shù)測(cè)試研究含氟量對(duì)于聚合物電解質(zhì)的電學(xué)性能的影響,最后通過(guò)應(yīng)力應(yīng)變測(cè)試分析聚合物電解質(zhì)的力學(xué)性能�；诩谆┧崃□ズ洼d流子與EO比值對(duì)聚合物電解質(zhì)的離子電導(dǎo)率的影響,制備了一系列含氟量不同的Li+/EO=1:27的聚苯乙烯磺酸鋰電解質(zhì),通過(guò)同樣的測(cè)試方法對(duì)合成的聚合物電解質(zhì)的結(jié)構(gòu),熱穩(wěn)定性,力學(xué)性能,電學(xué)性能進(jìn)行了分析。有研究表明納米顆粒的加入可以有效地提高聚合物電解質(zhì)的離子電導(dǎo)率和機(jī)械性能,在Li+/EO=1:27的基礎(chǔ)上,合成了含不同納米二氧化硅量的聚苯乙烯磺酸鋰電解質(zhì),通過(guò)同樣的分析測(cè)試方法對(duì)聚合物的結(jié)構(gòu)和性能進(jìn)行了分析,研究了納米二氧化硅含量對(duì)于聚合物電解質(zhì)的玻璃化轉(zhuǎn)變溫度,離子電導(dǎo)率的影響。通過(guò)差示掃描量熱對(duì)聚合物的玻璃化轉(zhuǎn)變溫度進(jìn)行測(cè)試,結(jié)果顯示隨著聚合物結(jié)構(gòu)中甲基丙烯酸六氟丁酯和納米二氧化硅含量的上升增加,聚合物體系的玻璃化轉(zhuǎn)變溫度升高;三種體系中的聚合物電解質(zhì)的鋰離子遷移數(shù)隨體系中甲基丙烯酸六氟丁酯或納米二氧化硅含量上升而上升;通過(guò)交流阻抗譜測(cè)試聚合物電解質(zhì)的電導(dǎo)率可知,對(duì)于Li+/EO=1:18的聚合物含氟量為30%時(shí)有最高的電導(dǎo)率,為8.7×10-7S/cm,對(duì)于Li+/EO=1:27的聚合物含氟量為20%時(shí)有最高的電導(dǎo)率,為6.9×10-6S/cm,其離子電導(dǎo)率隨著反應(yīng)物中甲基丙烯酸六氟丁酯含量的增加先升高后下降,含納米二氧化硅量為0.6%的電解質(zhì)電導(dǎo)率最大,達(dá)到7.7×10-5S/cm,聚合物電解質(zhì)的鋰離子遷移數(shù)均隨著氟含量或納米二氧化硅含量的上升而增加。聚合物電解質(zhì)的機(jī)械性能滿足實(shí)際應(yīng)用。
[Abstract]:Electric power equipment is one of the greatest challenges that mankind faces in this century. The non-aqueous liquid electrolyte of the traditional lithium-ion battery has made great progress in the past 20 years, but because of the inherent properties of the liquid electrolyte, there is a hidden danger to the safety of the liquid electrolyte. Moreover, the energy density of liquid electrolyte can not meet the practical application. Compared with liquid lithium-ion battery, polymer lithium-ion battery with polymer as electrolyte has better practicability and safety, so it can be used in a more wide range of fields. The traditional solid-state polymer electrolytes are double ionic conductors. The concentration polarization caused by the migration of anions and cations leads to poor performance of the batteries. Single-ion polymer electrolytes avoid the defects of double-ion conductors while maintaining the advantages of solid-state polymer electrolytes, but at present the conductivity of single-ion polymer electrolytes is low, which can not meet the actual needs of lithium-ion batteries. In order to improve the conductivity of polymer electrolytes, three kinds of solid-state single-ion polymer electrolyte films were designed and synthesized, and their properties were characterized. In this paper, a series of lithium poly (p-styrene sulfonic acid) electrolytes with different fluoride contents of Li / EO=1:18 were synthesized. The structure of polymer electrolyte was characterized by energy spectrum and other analytical methods. Then the glass transition temperature and characterization of polymer electrolyte were analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The effect of fluoride content on the electrical properties of polymer electrolytes was studied by lithium ion migration number test. Finally, the mechanical properties of polymer electrolytes were analyzed by stress-strain test. Based on the influence of hexafluorobutyl methacrylate and carrier-to-EO ratio on ionic conductivity of polymer electrolytes, a series of lithium polystyrene sulfonic acid electrolytes with different fluoride contents in Li / EO=1:27 were prepared. The structure, thermal stability, mechanical and electrical properties of the synthesized polymer electrolyte were analyzed by the same test method. It has been shown that the addition of nano-particles can effectively improve the ionic conductivity and mechanical properties of polymer electrolytes. On the basis of Li / EO=1:27, lithium polystyrene sulfonate electrolytes with different amount of nano-silicon dioxide were synthesized. The structure and properties of the polymer were analyzed by the same method. The effect of nano-silica content on the glass transition temperature and ionic conductivity of polymer electrolyte was studied. The glass transition temperature of the polymer was measured by differential scanning calorimetry. The results showed that the glass transition temperature of the polymer system increased with the increase of the content of hexafluorobutyl methacrylate and nano-silica in the polymer structure. The lithium ion migration number of polymer electrolytes in the three systems increased with the increase of hexafluoro-butyl methacrylate or nano-Sio _ 2 content. The conductivity of polymer electrolyte tested by AC impedance spectroscopy shows that the highest conductivity of Li / EO=1:18 is 8.7 脳 10 ~ (- 7) S 路cm ~ (- 1) when the fluorine content of polymer is 30%. When the fluorine content of Li / EO=1:27 polymer is 20%, it has the highest conductivity, which is 6.9 脳 10-6S 路cm ~ (- 1). The ionic conductivity of the polymer increases first and then decreases with the increase of the content of hexafluorobutyl methacrylate in the reactants. The electrolyte containing 0.6% nano-silicon dioxide has the highest conductivity, reaching 7.7 脳 10-5 S 路cm ~ (- 1). The lithium ion migration number of polymer electrolyte increases with the increase of fluorine content or nano-Sio _ 2 content. The mechanical properties of polymer electrolytes meet the practical application.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O646;O631.3
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本文編號(hào)：2452756