含氟聚苯乙烯磺酸锂电解质的制备与性能研究
发布时间：2019-04-02 17:35
【摘要】：电力设备是本世纪人类遇到的最大的挑战之一。传统锂离子电池的非水液态电解质在过去的二十年有很大的研究进展,但是由于液态电解质的固有属性使得液态电解质存在安全隐患,而且液态电解质的能量密度也无法满足实际应用。相比于液态锂离子电池,采用聚合物作电解质的聚合物锂离子电池具有更好的实用性与安全性,从而能够应用于更加广泛的领域。传统的固态聚合物电解质是双离子导体,阴离子与阳离子移动的造成浓差极化现象使得电池性能均不佳。单离子聚合物电解质在保持固态聚合物电解质的优点的基础下避免了双离子导体的缺陷,但是目前单离子聚合物电解质电导率低,不能满足锂离子电池的实际需要。本论文为了提高聚合物电解质的电导率,设计合成三种固态单离子聚合物电解质薄膜的合成及性能表征。本文首先合成了一系列Li+/EO=1:18的含氟量不同的聚对苯乙烯磺酸锂电解质,通过核磁共振氢谱,红外光谱,扫描电镜,能谱等分析测试方法对聚合物电解质的结构进行了表征,随后通过差示扫描量热分析,热重分析对聚合物电解质的玻璃化转变温度和定性进行了分析,通过交流阻抗谱,锂离子迁移数测试研究含氟量对于聚合物电解质的电学性能的影响,最后通过应力应变测试分析聚合物电解质的力学性能。基于甲基丙烯酸六氟丁酯和载流子与EO比值对聚合物电解质的离子电导率的影响,制备了一系列含氟量不同的Li+/EO=1:27的聚苯乙烯磺酸锂电解质,通过同样的测试方法对合成的聚合物电解质的结构,热稳定性,力学性能,电学性能进行了分析。有研究表明纳米颗粒的加入可以有效地提高聚合物电解质的离子电导率和机械性能,在Li+/EO=1:27的基础上,合成了含不同纳米二氧化硅量的聚苯乙烯磺酸锂电解质,通过同样的分析测试方法对聚合物的结构和性能进行了分析,研究了纳米二氧化硅含量对于聚合物电解质的玻璃化转变温度,离子电导率的影响。通过差示扫描量热对聚合物的玻璃化转变温度进行测试,结果显示随着聚合物结构中甲基丙烯酸六氟丁酯和纳米二氧化硅含量的上升增加,聚合物体系的玻璃化转变温度升高;三种体系中的聚合物电解质的锂离子迁移数随体系中甲基丙烯酸六氟丁酯或纳米二氧化硅含量上升而上升;通过交流阻抗谱测试聚合物电解质的电导率可知,对于Li+/EO=1:18的聚合物含氟量为30%时有最高的电导率,为8.7×10-7S/cm,对于Li+/EO=1:27的聚合物含氟量为20%时有最高的电导率,为6.9×10-6S/cm,其离子电导率随着反应物中甲基丙烯酸六氟丁酯含量的增加先升高后下降,含纳米二氧化硅量为0.6%的电解质电导率最大,达到7.7×10-5S/cm,聚合物电解质的锂离子迁移数均随着氟含量或纳米二氧化硅含量的上升而增加。聚合物电解质的机械性能满足实际应用。
[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.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O646;O631.3
，
本文编号：2452756
[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.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O646;O631.3
，
本文编号：2452756
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