CN106129468A - A kind of preparation method of single-ion polymer gel electrolyte materials - Google Patents

A kind of preparation method of single-ion polymer gel electrolyte materials Download PDF

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CN106129468A
CN106129468A CN201610555927.0A CN201610555927A CN106129468A CN 106129468 A CN106129468 A CN 106129468A CN 201610555927 A CN201610555927 A CN 201610555927A CN 106129468 A CN106129468 A CN 106129468A
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李瑀
张盼盼
封伟
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Abstract

本发明涉及一种单离子聚合物凝胶电解质材料的制备方法,将硼酸和氢氧化锂溶于去离子水中,油浴锅中加热;将一缩二丙二醇水溶液加入溶液中,升温,搅拌进行聚合反应;在聚合体系中加环己烷,利用共沸除去体系中的水,得到的白色沉淀为聚合产物;将聚合产物过滤收集,在真空干燥,得到白色粉末,即为单离子聚合物电解质材料;将聚合物电解质材料和聚偏氟乙烯‑六氟丙烯)共聚物溶于二甲基甲酰胺中,再加热使溶剂挥发得到电解质膜;将电解质膜在电解液碳酸丙烯酯中浸泡,得到单离子聚合物凝胶电解质膜。本发明制备方法简单易行,离子导电率提高到了1.2~2.0S·cm‑1,锂离子迁移数提高到了0.85~0.91。

The invention relates to a preparation method of a single-ion polymer gel electrolyte material, which comprises dissolving boric acid and lithium hydroxide in deionized water and heating in an oil bath; adding dipropylene glycol aqueous solution into the solution, raising the temperature, and stirring to carry out polymerization Reaction; add cyclohexane to the polymerization system, use azeotrope to remove water in the system, and the obtained white precipitate is the polymerization product; collect the polymerization product by filtration and dry it in vacuum to obtain a white powder, which is the single-ion polymer electrolyte material Dissolve the polymer electrolyte material and polyvinylidene fluoride-hexafluoropropylene) copolymer in dimethylformamide, and then heat to volatilize the solvent to obtain an electrolyte membrane; soak the electrolyte membrane in the electrolyte propylene carbonate to obtain a single Ionic polymer gel electrolyte membrane. The preparation method of the invention is simple and easy, the ion conductivity is increased to 1.2-2.0 S·cm -1 , and the lithium ion migration number is increased to 0.85-0.91.

Description

一种单离子聚合物凝胶电解质材料的制备方法A kind of preparation method of single ion polymer gel electrolyte material

技术领域technical field

本发明涉及一种单离子聚合物凝胶电解质材料的制备方法,具体来说是由一缩二丙二醇、硼酸和氢氧化锂在水溶液中聚合,再通过成膜和凝胶化过程的制备方法。The invention relates to a preparation method of a single-ion polymer gel electrolyte material, specifically, a preparation method in which dipropylene glycol, boric acid and lithium hydroxide are polymerized in an aqueous solution, and then go through the process of film formation and gelation.

技术背景technical background

与传统的二次电池(镍氢电池、镍镉电池等)相比,锂离子二次电池具有比能量高、循环寿命长、环境友好等优点,因此成为一种重要的化学电源。但是,传统的锂离子电池使用的是易挥发的有机电解液,比如碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、乙烯碳酸酯(EC)等,虽然具有很高的离子导电率,但是由于其易燃易挥发,在锂离子电池的使用者存在诸多安全隐患(如燃烧、爆炸、泄漏等)。为了克服这个缺陷,人们提出了用聚合物电解质来替代电解液(吴宇平,戴晓兵,马军旗,程预江《锂离子电池—应用与实践》.北京化学工业出版社,2004年,pp.301)。Compared with traditional secondary batteries (Ni-MH batteries, Ni-Cd batteries, etc.), Li-ion secondary batteries have the advantages of high specific energy, long cycle life, and environmental friendliness, and thus become an important chemical power source. However, traditional lithium-ion batteries use volatile organic electrolytes, such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), etc., although they have high ionic conductivity , but because it is flammable and volatile, there are many safety hazards (such as combustion, explosion, leakage, etc.) in the users of lithium-ion batteries. In order to overcome this defect, it has been proposed to replace the electrolyte with a polymer electrolyte (Wu Yuping, Dai Xiaobing, Ma Junqi, Cheng Yujiang "Lithium Ion Batteries-Application and Practice". Beijing Chemical Industry Press, 2004, pp.301 ).

但是单纯的聚合物电解质存在两个问题:一是聚合物电解质的锂离子迁移数很低,充放电过程中容易产生浓度差,形成锂枝晶,造成电池的短路;二是聚合物电解质离子导电率很低,目前单纯的聚合物电解质的离子导电率还不能满足锂电池的实际应用。为了解决锂离子迁移数低的问题,提出了单离子聚合物电解质的概念,是指将阴离子固定在聚合物主链上,仅有阳离子发生迁移。这种单离子导体阴离子被固定在聚合物主链上,在充放电过程中不会因为阴阳离子迁移速度不同而产生浓差极化,因此具有很高的锂离子迁移数,能够有效的避免锂枝晶的形成,提高锂离子电池的性能。为了解决离子导电率低的问题,提出了凝胶聚合物电解质的概念,就是在聚合物体系中添加极少量的有机电解液,从而提高其离子导电率。因此,单离子聚合物凝胶电解质材料的出现,能够从锂离子迁移数和离子导电率两个方面改善锂电池的性能。However, there are two problems with the pure polymer electrolyte: one is that the lithium ion migration number of the polymer electrolyte is very low, and it is easy to produce a concentration difference during charging and discharging, forming lithium dendrites and causing a short circuit of the battery; the other is that the polymer electrolyte ion conduction The rate is very low, and the ionic conductivity of pure polymer electrolytes cannot meet the practical application of lithium batteries at present. In order to solve the problem of low migration number of lithium ions, the concept of single-ion polymer electrolyte is proposed, which means that anions are fixed on the polymer main chain, and only cations migrate. This kind of single-ion conductor anion is fixed on the polymer main chain, and there will be no concentration polarization due to the difference in the migration speed of anion and cation during the charge and discharge process, so it has a high lithium ion migration number and can effectively avoid lithium ions. The formation of dendrites improves the performance of lithium-ion batteries. In order to solve the problem of low ionic conductivity, the concept of gel polymer electrolyte is proposed, which is to add a very small amount of organic electrolyte to the polymer system to improve its ionic conductivity. Therefore, the emergence of single-ion polymer gel electrolyte materials can improve the performance of lithium batteries from two aspects of lithium ion migration number and ion conductivity.

目前,国内外许多研究者在单离子聚合物凝胶电解质方面做了许多研究工作。Zhu等用PVA与硼酸、草酸进行络合聚合反应得到单离子聚合物(Zhu Y S,Wang X J,Hou Y Y,et al.A new single-ion polymer electrolyte based on polyvinyl alcohol forlithium ion batteries[J].Electrochimica Acta,2013,87(1):113-118.)但是,由于PVA是半结晶结构,室温下锂离子的迁移数接近1,离子导电率仅能达到6.11×10-6s cm-1。Wang等用酒石酸与硼酸络合反应得到了单离子聚合物(Wang X,Liu Z,Kong Q,et al.Asingle-ion gel polymer electrolyte based on polymeric lithium tartaric acidborate and its superior battery performance[J].Solid State Ionics,2014,262(9):747-753.)。由于聚合物上的醚氧键存在于环上,运动能力差,不利于锂离子的迁移,在室温下离子导电率可达到1.4×10-4s cm-1,锂离子迁移数接近1,但是倍率性能较差。为了使聚合过程简便,电解质性能优异,本发明首次在水溶液中合成一种主链上带有醚氧键的单离子聚合物结构,醚氧键的运动能力强,可以制备出性能良好的单离子聚合物凝胶电解质膜。At present, many researchers at home and abroad have done a lot of research work on single-ion polymer gel electrolytes. Zhu et al. used PVA, boric acid, and oxalic acid for complex polymerization to obtain single-ion polymers (Zhu YS, Wang XJ, Hou YY, et al. A new single-ion polymer electrolyte based on polyvinyl alcohol forlithium ion batteries[J]. Electrochimica Acta,2013,87(1):113-118.) However, due to the semi-crystalline structure of PVA, the migration number of lithium ions at room temperature is close to 1, and the ion conductivity can only reach 6.11×10 -6 s cm -1 . Wang et al. used tartaric acid and boric acid complexation reaction to obtain a single ion polymer (Wang X, Liu Z, Kong Q, et al.Asingle-ion gel polymer electrolyte based on polymeric lithium tartaric acidborate and its superior battery performance[J].Solid State Ionics, 2014, 262(9):747-753.). Because the ether oxygen bonds on the polymer exist on the ring, the mobility is poor, which is not conducive to the migration of lithium ions. At room temperature, the ionic conductivity can reach 1.4×10 -4 s cm -1 , and the lithium ion migration number is close to 1, but Magnification performance is poor. In order to make the polymerization process simple and the electrolyte performance excellent, the present invention synthesizes a single-ion polymer structure with ether oxygen bonds on the main chain for the first time in aqueous solution. The ether oxygen bonds have strong mobility and can prepare single-ion polymers with good performance. polymer gel electrolyte membrane.

发明内容Contents of the invention

为了解决现有技术的问题,本发明是用一缩二丙二醇、硼酸和氢氧化锂在水溶液中络合聚合,再通过成膜和凝胶化过程的制备出一种单离子聚合物凝胶电解质。In order to solve the problems of the prior art, the present invention uses dipropylene glycol, boric acid and lithium hydroxide in aqueous solution for complex polymerization, and then prepares a single-ion polymer gel electrolyte through film-forming and gelation processes .

本发明的具体技术方案如下:Concrete technical scheme of the present invention is as follows:

一种单离子聚合物凝胶电解质材料的制备方法:包括如下步骤:A preparation method of a single-ion polymer gel electrolyte material: comprising the steps of:

(1)将硼酸和氢氧化锂溶于去离子水中,硼酸和氢氧化锂两种物质的物质的量之比为1:1,油浴锅中加热;(1) Boric acid and lithium hydroxide are dissolved in deionized water, the ratio of the amount of boric acid and lithium hydroxide is 1:1, and heated in an oil bath;

(2)将一缩二丙二醇水溶液加入步骤(1)所得溶液中,升温,搅拌进行聚合反应;(2) Dipropylene glycol aqueous solution is added in the solution obtained in step (1), the temperature is raised, and the polymerization reaction is carried out with stirring;

(3)在聚合体系中加环己烷,利用共沸除去体系中的水,得到的白色沉淀为聚合产物;(3) Add cyclohexane in the polymerization system, utilize azeotropic removal of water in the system, and the white precipitate obtained is the polymerization product;

(4)将聚合产物过滤收集,在真空干燥,得到白色粉末,即为单离子聚合物电解质材料;(4) The polymer product is collected by filtration, and dried in vacuum to obtain a white powder, which is a single-ion polymer electrolyte material;

(5)将聚合物电解质材料和聚偏氟乙烯-六氟丙烯)共聚物按1:2的摩尔比溶于二甲基甲酰胺中,再加热使溶剂挥发得到电解质膜;将电解质膜在电解液碳酸丙烯酯中浸泡,得到单离子聚合物凝胶电解质膜。(5) Dissolve the polymer electrolyte material and polyvinylidene fluoride-hexafluoropropylene copolymer in dimethylformamide at a molar ratio of 1:2, and then heat to volatilize the solvent to obtain an electrolyte membrane; soaked in liquid propylene carbonate to obtain a single-ion polymer gel electrolyte membrane.

所述步骤(1)中硼酸和氢氧化锂水溶液的浓度为0.1~2mol/L,加热温度为40~60℃。The concentration of boric acid and lithium hydroxide aqueous solution in the step (1) is 0.1-2 mol/L, and the heating temperature is 40-60°C.

所述步骤(2)中一缩二丙二醇水溶液的浓度为0.2~4mol/L,一缩二丙二醇摩尔数等于硼酸摩尔数的两倍。The concentration of the dipropylene glycol aqueous solution in the step (2) is 0.2 to 4 mol/L, and the moles of dipropylene glycol are equal to twice the moles of boric acid.

所述步骤(2)中聚合反应时间为16~24h,反应温度为80℃~100℃.The polymerization reaction time in the step (2) is 16 to 24 hours, and the reaction temperature is 80°C to 100°C.

所述步骤(3)中按每100mL水中加入60~80mL环己烷的比例加入环己烷。In the step (3), cyclohexane is added in a ratio of 60 to 80 mL of cyclohexane per 100 mL of water.

所述步骤(4)真空干燥的温度为50~60℃,真空度为-0.1~-0.08MPa、时间为12~24h。In the step (4), the vacuum drying temperature is 50-60° C., the vacuum degree is -0.1-0.08 MPa, and the time is 12-24 hours.

对单离子聚合物凝胶电解质膜进行电性能测试,离子导电率提高到了1.2~2.0S·cm-1,锂离子迁移数提高到了0.85~0.91。The electrical properties of the single-ion polymer gel electrolyte membrane were tested, and the ion conductivity was increased to 1.2-2.0 S·cm -1 , and the lithium ion migration number was increased to 0.85-0.91.

本发明的有益效果:本发明首次以硼酸和一缩二乙二醇水溶液(单体摩尔比例为1:2,溶液浓度为0.5~1mol/L)在80-100℃的温度下合成一种主链上带有醚氧键的单离子聚合物结构,如附图1、附图2所示。实验中选择聚偏氟乙烯-六氟丙烯共聚物做成膜剂,碳酸丙烯酯做增塑剂,制备方法简单易行,操作简单,通过调整反应物的浓度和反应温度得到纯净的单离子聚合物,在通过成膜和凝胶化过程得到性能良好的单离子聚合物凝胶电解质。Beneficial effects of the present invention: the present invention is the first to use boric acid and diethylene glycol aqueous solution (monomer molar ratio is 1:2, solution concentration is 0.5-1mol/L) to synthesize a main The single-ion polymer structure with ether oxygen bonds on the chain is shown in accompanying drawing 1 and accompanying drawing 2. In the experiment, polyvinylidene fluoride-hexafluoropropylene copolymer was selected as film-forming agent and propylene carbonate as plasticizer. The preparation method is simple and easy to operate. Pure single-ion polymerization can be obtained by adjusting the concentration of reactants and reaction temperature. Through the process of film formation and gelation, a single-ion polymer gel electrolyte with good performance is obtained.

附图说明Description of drawings

图1浓度为0.5mol/L的硼酸和一缩二乙二醇在80℃条件下聚合得到单离子聚合物的红外表征图;Fig. 1 concentration is that boric acid and diethylene glycol of 0.5mol/L are polymerized under the condition of 80 ℃ to obtain the infrared characterization figure of single ion polymer;

图2浓度为0.5mol/L的硼酸和一缩二乙二醇在80℃条件下聚合得到单离子聚合物的核磁表征图;Fig. 2 concentration is the NMR characterization diagram of the single-ion polymer obtained by polymerization of boric acid and diethylene glycol at 80°C with a concentration of 0.5mol/L;

图3浓度为0.5mol/L的硼酸和一缩二乙二醇在80℃条件下聚合得到单离子聚合物凝胶电解质膜离子导电率表征图。Figure 3 is a characterization diagram of the ionic conductivity of the single-ion polymer gel electrolyte membrane obtained by polymerization of boric acid and diethylene glycol at a concentration of 0.5 mol/L at 80°C.

具体实施方式detailed description

为了使本发明的优点、技术方案及目的更加明白,下面结合实例对本发明进行进一步的说明。下面给出本发明的实施例,是对本发明的进一步说明,而不是限制本发明的范围。In order to make the advantages, technical solutions and objectives of the present invention more clear, the present invention will be further described below in conjunction with examples. The following examples of the present invention are given to further illustrate the present invention, rather than limit the scope of the present invention.

实施例1Example 1

(1)将0.01mol硼酸和氢氧化锂溶于100ml的去离子水中(浓度为0.1mol/L),60℃搅拌至完全溶解;(1) Dissolve 0.01mol of boric acid and lithium hydroxide in 100ml of deionized water (concentration: 0.1mol/L), and stir at 60°C until completely dissolved;

(2)将100ml浓度为0.2mol/L的一缩二丙二醇水溶液逐滴加入步骤(1)所得溶液中,升温至80℃,搅拌进行聚合反应,反应16小时;(2) Add 100 ml of dipropylene glycol aqueous solution with a concentration of 0.2 mol/L dropwise into the solution obtained in step (1), raise the temperature to 80° C., stir for polymerization, and react for 16 hours;

(3)在聚合体系中按每100mL水中加入60mL环己烷的比例加入环己烷,利用共沸原理除去体系中的水,得到的白色沉淀为聚合产物;(3) Add cyclohexane in the polymerization system at a ratio of 60 mL cyclohexane per 100 mL of water, and use the azeotropic principle to remove the water in the system, and the white precipitate obtained is the polymerization product;

(4)将聚合产物过滤收集,在50℃、真空度为-0.08MPa的条件下真空干燥24小时,得到白色粉末,即为单离子聚合物电解质材料,结果表征如图1、2所示。(4) The polymerized product was collected by filtration, and vacuum-dried for 24 hours at 50°C and a vacuum degree of -0.08MPa to obtain a white powder, which is a single-ion polymer electrolyte material. The characterization of the results is shown in Figures 1 and 2.

(5)将聚合物电解质材料和聚偏氟乙烯-六氟丙烯共聚物按1:2的摩尔比溶于二甲基甲酰胺中,使溶剂挥发得到电解质膜,将电解质膜在电解液碳酸丙烯酯中浸泡,得到单离子聚合物凝胶电解质。(5) Dissolve the polymer electrolyte material and polyvinylidene fluoride-hexafluoropropylene copolymer in dimethylformamide at a molar ratio of 1:2, volatilize the solvent to obtain an electrolyte membrane, and place the electrolyte membrane in the electrolyte solution of propylene carbonate Soaked in ester to obtain single-ion polymer gel electrolyte.

对单离子聚合物凝胶电解质进行电性能测试,其中离子导电率表征如图3所示,计算出室温下离子导电率为2.0×10-4S·cm-1,锂离子迁移数为0.91。The electrical properties of the single-ion polymer gel electrolyte were tested, and the ionic conductivity is shown in Figure 3. The calculated ionic conductivity at room temperature was 2.0×10 -4 S·cm -1 , and the lithium ion migration number was 0.91.

实施例2Example 2

(1)将0.03mol硼酸和氢氧化锂溶于60ml的去离子水中(浓度为0.5mol/L),40℃搅拌至完全溶解;(1) Dissolve 0.03mol of boric acid and lithium hydroxide in 60ml of deionized water (concentration: 0.5mol/L), and stir at 40°C until completely dissolved;

(2)将60ml浓度为1mol/L的一缩二丙二醇水溶液滴加入步骤(1)所得溶液中,升温至100℃,搅拌进行聚合反应,反应24小时;(2) Add 60 ml of dipropylene glycol aqueous solution with a concentration of 1 mol/L dropwise into the solution obtained in step (1), heat up to 100° C., stir for polymerization, and react for 24 hours;

(3)在聚合体系中按每100mL水中加入80mL环己烷的比例加入环己烷,利用共沸原理除去体系中的水,得到的白色沉淀为聚合产物;(3) Add cyclohexane in the polymerization system at a ratio of 80 mL cyclohexane per 100 mL of water, and use the azeotropic principle to remove the water in the system, and the white precipitate obtained is the polymerization product;

(4)将聚合反应产物过滤收集,在60℃、真空度为-0.01MPa的条件下真空干燥12小时,得到白色粉末,即为单离子聚合物电解质材料。(4) The polymerization reaction product was collected by filtration, and vacuum-dried for 12 hours at 60° C. and a vacuum degree of −0.01 MPa to obtain a white powder, which is a single-ion polymer electrolyte material.

(5)将聚合物电解质材料和聚偏氟乙烯-六氟丙烯共聚物按1:2的摩尔比溶于二甲基甲酰胺中,使溶剂挥发得到电解质膜,将电解质膜在电解液碳酸丙烯酯中浸泡,得到单离子聚合物凝胶电解质。(5) Dissolve the polymer electrolyte material and polyvinylidene fluoride-hexafluoropropylene copolymer in dimethylformamide at a molar ratio of 1:2, volatilize the solvent to obtain an electrolyte membrane, and place the electrolyte membrane in the electrolyte solution of propylene carbonate Soaked in ester to obtain single-ion polymer gel electrolyte.

对单离子聚合物凝胶电解质进行电性能测试,计算出室温下的离子导电率为1.8×10-4S·cm-1,锂离子迁移数为0.88。The electrical properties of the single-ion polymer gel electrolyte were tested, and the calculated ionic conductivity at room temperature was 1.8×10 -4 S·cm -1 , and the lithium ion migration number was 0.88.

实施例3Example 3

(1)将0.1mol硼酸和氢氧化锂溶于100ml的去离子水中(浓度为1mol/L),60℃搅拌至完全溶解;(1) Dissolve 0.1mol boric acid and lithium hydroxide in 100ml deionized water (concentration is 1mol/L), stir at 60°C until completely dissolved;

(2)将100ml浓度为2mol/L的一缩二丙二醇水溶液滴加入步骤(1)所得溶液中,升温至80℃,搅拌进行聚合反应,反应21小时;(2) Add 100 ml of dipropylene glycol aqueous solution with a concentration of 2 mol/L dropwise into the solution obtained in step (1), heat up to 80° C., stir for polymerization, and react for 21 hours;

(3)在聚合体系中按每100mL水中加入60mL环己烷的比例加入环己烷,利用共沸原理除去体系中的水,得到的白色沉淀为聚合产物;(3) Add cyclohexane in the polymerization system at a ratio of 60 mL cyclohexane per 100 mL of water, and use the azeotropic principle to remove the water in the system, and the white precipitate obtained is the polymerization product;

(4)将聚合产物过滤收集,在60℃、真空度为-0.04MPa的条件下真空干燥20小时,得到白色粉末,即为单离子聚合物电解质材料。(4) The polymerized product was collected by filtration, and vacuum-dried for 20 hours at 60° C. and a vacuum degree of −0.04 MPa to obtain a white powder, which is a single-ion polymer electrolyte material.

(5)将聚合物电解质材料和聚偏氟乙烯-六氟丙烯共聚物按1:2的摩尔比溶于二甲基甲酰胺中,使溶剂挥发得到电解质膜,将电解质膜在电解液碳酸丙烯酯中浸泡,得到单离子聚合物凝胶电解质。(5) Dissolve the polymer electrolyte material and polyvinylidene fluoride-hexafluoropropylene copolymer in dimethylformamide at a molar ratio of 1:2, volatilize the solvent to obtain an electrolyte membrane, and place the electrolyte membrane in the electrolyte solution of propylene carbonate Soaked in ester to obtain single-ion polymer gel electrolyte.

对单离子聚合物凝胶电解质进行电性能测试,计算出室温下的离子导电率为1.5×10-4S·cm-1,锂离子迁移数为0.89。The electrical properties of the single-ion polymer gel electrolyte were tested, and the calculated ionic conductivity at room temperature was 1.5×10 -4 S·cm -1 , and the lithium ion migration number was 0.89.

实施例4Example 4

(1)将0.15mol硼酸和氢氧化锂溶于100ml的去离子水中(浓度为1.5mol/L),50℃搅拌至完全溶解;(1) Dissolve 0.15mol of boric acid and lithium hydroxide in 100ml of deionized water (concentration: 1.5mol/L), and stir at 50°C until completely dissolved;

(2)将100ml浓度为3mol/L的一缩二丙二醇水溶液滴加入步骤(1)所得溶液中,升温至90℃,搅拌进行聚合反应,反应24小时;(2) Add 100 ml of dipropylene glycol aqueous solution with a concentration of 3 mol/L dropwise into the solution obtained in step (1), heat up to 90° C., stir for polymerization, and react for 24 hours;

(3)在聚合体系中按每100mL水中加入70mL环己烷的比例加入环己烷,利用共沸原理除去体系中的水,得到的白色沉淀为聚合产物;(3) Add cyclohexane in the polymerization system at a ratio of 70 mL cyclohexane per 100 mL of water, and use the azeotropic principle to remove the water in the system, and the white precipitate obtained is the polymerization product;

(4)将聚合产物过滤收集,在50℃、真空度为-0.08MPa的条件下真空干燥20小时,得到白色粉末,即为单离子聚合物电解质材料。(4) The polymerized product was collected by filtration, and vacuum-dried for 20 hours at 50° C. and a vacuum degree of −0.08 MPa to obtain a white powder, which is a single-ion polymer electrolyte material.

(5)将聚合物电解质材料和聚偏氟乙烯-六氟丙烯共聚物按1:2的摩尔比溶于二甲基甲酰胺中,使溶剂挥发得到电解质膜,将电解质膜在电解液碳酸丙烯酯中浸泡,得到单离子聚合物凝胶电解质。(5) Dissolve the polymer electrolyte material and polyvinylidene fluoride-hexafluoropropylene copolymer in dimethylformamide at a molar ratio of 1:2, volatilize the solvent to obtain an electrolyte membrane, and place the electrolyte membrane in the electrolyte solution of propylene carbonate Soaked in ester to obtain single-ion polymer gel electrolyte.

对单离子聚合物凝胶电解质进行电性能测试,计算出室温下的离子导电率为1.8×10-4S·cm-1,锂离子迁移数为0.85。The electrical properties of the single-ion polymer gel electrolyte were tested, and the calculated ionic conductivity at room temperature was 1.8×10 -4 S·cm -1 , and the lithium ion migration number was 0.85.

实施例5Example 5

(1)将0.2mol硼酸和氢氧化锂溶于100ml的去离子水中(浓度为2mol/L),50℃搅拌至完全溶解;(1) Dissolve 0.2mol of boric acid and lithium hydroxide in 100ml of deionized water (concentration is 2mol/L), stir at 50°C until completely dissolved;

(2)将100ml浓度为4mol/L的一缩二丙二醇水溶液滴加入步骤(1)所得溶液中,升温至80℃,搅拌进行聚合反应,反应22小时;(2) Add 100ml of dipropylene glycol aqueous solution with a concentration of 4mol/L dropwise into the solution obtained in step (1), heat up to 80°C, stir and carry out polymerization reaction, and react for 22 hours;

(3)在聚合体系中按每100mL水中加入60mL环己烷的比例加入环己烷,利用共沸原理除去体系中的水,得到的白色沉淀为聚合产物;(3) Add cyclohexane in the polymerization system at a ratio of 60 mL cyclohexane per 100 mL of water, and use the azeotropic principle to remove the water in the system, and the white precipitate obtained is the polymerization product;

(4)将聚合产物过滤收集,在55℃、真空度为-0.08MPa的条件下真空干燥23小时,得到白色粉末,即为单离子聚合物电解质材料。(4) The polymerized product was collected by filtration, and vacuum-dried for 23 hours at 55° C. and a vacuum degree of −0.08 MPa to obtain a white powder, which is a single-ion polymer electrolyte material.

(5)将聚合物电解质材料和聚偏氟乙烯-六氟丙烯共聚物按1:2的摩尔比溶于二甲基甲酰胺中,使溶剂挥发得到电解质膜,将电解质膜在电解液碳酸丙烯酯中浸泡,得到单离子聚合物凝胶电解质。(5) Dissolve the polymer electrolyte material and polyvinylidene fluoride-hexafluoropropylene copolymer in dimethylformamide at a molar ratio of 1:2, volatilize the solvent to obtain an electrolyte membrane, and place the electrolyte membrane in the electrolyte solution of propylene carbonate Soaked in ester to obtain single-ion polymer gel electrolyte.

对单离子聚合物凝胶电解质进行电性能测试,计算出室温下的离子导电率为1.2×10-4S·cm-1,锂离子迁移数为0.88。The electrical properties of the single-ion polymer gel electrolyte were tested, and the calculated ionic conductivity at room temperature was 1.2×10 -4 S·cm -1 , and the lithium ion migration number was 0.88.

本发明公开和提出用一缩二丙二醇、硼酸和氢氧化锂在水溶液中络合聚合,再通过成膜和凝胶化过程的制备出一种单离子聚合物凝胶电解质的方法,本领域技术人员可通过借鉴本文内容,适当改变原料和工艺路线等环节实现,尽管本发明的方法和制备技术已通过较佳实施例子进行了描述,相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和技术路线进行改动或重新组合,来实现最终的制备技术。特别需要指出的是,所有相类似的替换和改动对本领域技术人员来说是显而易见的,他们都被视为包括在本发明精神、范围和内容中。The present invention discloses and proposes a method for preparing a single-ion polymer gel electrolyte by complexing and polymerizing dipropylene glycol, boric acid and lithium hydroxide in an aqueous solution, and then preparing a single-ion polymer gel electrolyte through the process of film formation and gelation. Personnel can realize by referring to the contents of this article, appropriately changing links such as raw materials and process routes, although the method and preparation technology of the present invention have been described through preferred implementation examples, those skilled in the art can obviously achieve this without departing from the content, spirit and scope of the present invention. The methods and technical routes described in this paper are modified or recombined to realize the final preparation technology. In particular, it should be pointed out that all similar substitutions and modifications will be obvious to those skilled in the art, and they are all considered to be included in the spirit, scope and content of the present invention.

Claims (7)

1. a preparation method for single-ion polymer gel electrolyte materials, is characterized in that specifically comprising the following steps that
(1) boric acid and Lithium hydrate being dissolved in deionized water, the ratio of the amount of the material of boric acid and two kinds of materials of Lithium hydrate is 1:1, heats in oil bath pan;
(2) being added dropwise over by dipropylene glycol aqueous solution in step (1) gained solution, heat up, stirring carries out polyreaction;
(3) adding hexamethylene in polymerization system, utilize the water being azeotroped off in system, the white precipitate obtained is polymerizate;
(4) polymerizate is collected by filtration, in vacuum drying, obtains white powder, be single-ion polymer electrolyte;
(5) polymer electrolyte and Kynoar-hexafluoropropylene copolymer are dissolved in dimethyl methyl by the mol ratio of 1:2 In amide, reheat and make solvent volatilization obtain dielectric film;Dielectric film is soaked in electrolyte Allyl carbonate, obtains list Ionic polymer gel dielectric film.
2. method as claimed in claim 2, is characterized in that the concentration of described step (1) mesoboric acid and lithium hydroxide aqueous solution is 0.1~2mol/L, heating-up temperature is 40~60 DEG C.
3. method as claimed in claim 2, is characterized in that in described step (2), the concentration of dipropylene glycol aqueous solution is 0.2~4mol/L.
4. method as claimed in claim 2, is characterized in that the dipropylene glycol molal quantity twice equal to boric acid molal quantity.
5. method as claimed in claim 2, is characterized in that in described step (2), polymerization reaction time is 16~24h, reaction temperature Degree is 80 DEG C~100 DEG C.
6. method as claimed in claim 2, is characterized in that in described step (3) by adding 60~80mL rings in every 100mL water The ratio of hexane adds hexamethylene.
7. method as claimed in claim 2, is characterized in that described step (4) vacuum drying temperature is 50~60 DEG C, vacuum Degree is-0.1~-0.08MPa, the time is 12~24h.
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