技术领域technical field
本发明涉及一种电解质及其制备方法，特别是一种复合材料固态电解质及其制备方法，应用于锂离子二次电池技术领域。The invention relates to an electrolyte and a preparation method thereof, in particular to a composite material solid electrolyte and a preparation method thereof, which are applied in the technical field of lithium ion secondary batteries.
背景技术Background technique
锂离子电池作为一种绿色高效新能源，具有高电压、高能量密度、循环寿命长和无记忆效应等优点，已广泛应用于移动通信、笔记本电脑和微型摄像机等便携电子设备上,且在电动汽车动力电源、智能电网储能系统、微机电系统和航空航天等领域也显示出了良好的应用前景。电解质是锂电池的核心元件之一，不仅在正负电极之间起着传导电流和输运离子的作用，而且在很大程度上决定了电池的工作机制，是影响电池比能量、安全性、循环性能和倍率性能等的关键因素。As a green and efficient new energy source, lithium-ion batteries have the advantages of high voltage, high energy density, long cycle life, and no memory effect. They have been widely used in portable electronic devices such as mobile communications, notebook computers, and miniature cameras. Fields such as automotive power supplies, smart grid energy storage systems, micro-electromechanical systems, and aerospace have also shown good application prospects. Electrolyte is one of the core components of lithium batteries. It not only plays the role of conducting current and transporting ions between the positive and negative electrodes, but also determines the working mechanism of the battery to a large extent. It affects the specific energy, safety, and Key factors such as cycle performance and rate performance.
锂离子电池的电解质可分为液态电解质、固态电解质和固液复合电解质三大类。虽然液态电解质或固液复合型的凝胶聚合物电解质已大规模商用，但均含易渗漏的碳酸酯类有机溶剂，使得电池存在着火、爆炸等巨大安全隐患，特别是在滥用状态下尤为严重，如在热冲击、过充/放和短路时，电池使用时可能发生安全事故。因不含任何有机溶剂，且具有安全、与电极材料的反应活性低、循环性能良好、易于加工和封装等显著优点，高性能聚合物复合材料固态电解质是新一代锂电池不可或缺的组成部分。The electrolytes of lithium-ion batteries can be divided into three categories: liquid electrolytes, solid electrolytes, and solid-liquid composite electrolytes. Although liquid electrolytes or solid-liquid composite gel polymer electrolytes have been commercialized on a large scale, they all contain carbonate-based organic solvents that are easy to leak, which makes the batteries have huge safety hazards such as fire and explosion, especially when they are abused. Serious, such as thermal shock, overcharge/discharge and short circuit, safety accidents may occur when the battery is used. Because it does not contain any organic solvents, and has significant advantages such as safety, low reactivity with electrode materials, good cycle performance, easy processing and packaging, high-performance polymer composite solid-state electrolytes are an indispensable part of the new generation of lithium batteries .
全固态聚合物电解质电池具有能量密度高、制造简便、安全可靠和设计灵活等优点，成为未来化学电源的发展主流。但是，已有的聚氧化乙烯(PEO)、聚丙烯腈(PAN)和聚甲基丙烯酸甲酯(PMMA)基固态聚合物电解质的离子电导率和力学性能均较低，且成型过程中需使用大量的有机溶剂，成为制约其发展的主要因素。All-solid-state polymer electrolyte batteries have the advantages of high energy density, easy manufacturing, safety and reliability, and flexible design, and will become the mainstream of future chemical power supply development. However, the existing polyethylene oxide (PEO), polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA)-based solid polymer electrolytes have low ionic conductivity and mechanical properties, and need to use A large amount of organic solvents has become the main factor restricting its development.
发明内容Contents of the invention
为了克服已有技术存在的不足，本发明提供一种聚合物复合材料固态电解质及其制备方法，所制的复合材料不仅具有离子电导率高、力学性能优良的优点，而且松弛时间短，其成型工艺简单且符合绿色环保要求。In order to overcome the deficiencies in the prior art, the present invention provides a polymer composite solid electrolyte and a preparation method thereof. The composite material not only has the advantages of high ionic conductivity and excellent mechanical properties, but also has a short relaxation time and is easy to form. The process is simple and meets the requirements of green environmental protection.
为达到上述发明创造目的，本发明采用下述技术方案：In order to achieve the above invention creation purpose, the present invention adopts the following technical solutions:
一种聚合物复合材料固态电解质，由水性聚合物、锂盐、无机纳米粒子和多异氰酸酯诸原料组份组合而成，各原料组份按照组份干质量百分比配比如下：A polymer composite solid electrolyte, which is composed of water-based polymers, lithium salts, inorganic nanoparticles and polyisocyanate raw material components, the ratio of each raw material component according to the dry mass percentage of the component is as follows:
水性聚合物 40.0-80.0 wt%Waterborne polymer 40.0-80.0 wt%
锂盐 15.0-40.0 wt%Lithium salt 15.0-40.0 wt%
无机纳米填料 2.0-10.0 wt%Inorganic nanofiller 2.0-10.0 wt%
多异氰酸酯 3.0-10.0 wt%Polyisocyanate 3.0-10.0 wt%
上述水性聚合物优选采用聚乙烯醇、聚醋酸乙烯－乙烯乳胶粉和羧甲基纤维素中的任意一种或任意几种的混合物。The above-mentioned water-based polymer is preferably any one or a mixture of any of polyvinyl alcohol, polyvinyl acetate-ethylene latex powder and carboxymethyl cellulose.
上述锂盐优选采用高氯酸锂、碳酸锂、硫酸锂和硝酸锂中的任意一种或任意几种的混合物。The above-mentioned lithium salt is preferably any one or a mixture of any of lithium perchlorate, lithium carbonate, lithium sulfate and lithium nitrate.
上述无机纳米填料优选采用粒径小于100纳米的二氧化硅、二氧化钛和碳酸钙中的任意一种纳米粒子填料或任意几种纳米粒子填料的混合物。The above-mentioned inorganic nano-filler is preferably any nano-particle filler or a mixture of any several nano-particle fillers with a particle size of less than 100 nanometers among silica, titanium dioxide and calcium carbonate.
上述多异氰酸酯优选采用可水分散聚合多异氰酸酯和平均官能度不小于2.85的高官能度聚合多异氰酸酯中的任意一种或其二者的混合物。The above-mentioned polyisocyanate is preferably any one of water-dispersible polymeric polyisocyanate and high-functionality polymeric polyisocyanate with an average functionality of not less than 2.85 or a mixture of both.
一种本发明聚合物复合材料固态电解质的制备方法，基于水溶液浇铸法，各原料组份按照组份干质量百分比配比，使用60～80wt%的水性聚合物、10～40wt%的锂盐、2.0～8.0 wt%的无机纳米填料和2.0～8.0 wt%的多异氰酸酯交联剂作为原料制备聚合物复合材料固态电解质，具体步骤为：A method for preparing a polymer composite solid electrolyte of the present invention is based on an aqueous solution casting method, and the raw material components are proportioned according to the dry mass percentage of the components, using 60-80wt% water-based polymer, 10-40wt% lithium salt, 2.0-8.0 wt% of inorganic nanofillers and 2.0-8.0 wt% of polyisocyanate cross-linking agents are used as raw materials to prepare polymer composite solid electrolytes, and the specific steps are:
a．将水性聚合物和去离子水据1:10的质量配比加入反应釜中，缓慢升温至60-95℃，机械搅拌1-2小时使其变为分布均匀的水性聚合物溶液；a. Add water-based polymer and deionized water into the reaction kettle according to the mass ratio of 1:10, slowly raise the temperature to 60-95°C, and mechanically stir for 1-2 hours to make it into a uniformly distributed water-based polymer solution;
b．降温至50℃，并向在步骤a中制备的水性聚合物溶液中加入锂盐，进一步机械搅拌2-3小时，使锂盐完全溶解在水性聚合物溶液中；b. cooling to 50°C, and adding lithium salt to the aqueous polymer solution prepared in step a, and further mechanically stirring for 2-3 hours, so that the lithium salt is completely dissolved in the aqueous polymer solution;
c．继续降温至30-40℃，将含无机纳米填料的固含量为20 wt %的纳米粒子水性分散液缓缓加入在步骤b中制备的溶解锂盐的水性聚合物溶液中，在超声波与机械搅拌的共同作用下，混合2-3小时，使无机纳米填料分散于混合液中；c. Continue to cool down to 30-40°C, slowly add the aqueous dispersion of nanoparticles containing inorganic nanofillers with a solid content of 20 wt% to the aqueous polymer solution in which the lithium salt is dissolved prepared in step b, and stir under ultrasonic and mechanical stirring. Under the combined action of the mixture, mix for 2-3 hours to disperse the inorganic nano-filler in the mixture;
d．向在步骤c中制备的混合液中滴加聚合异氰酸酯，并搅拌15-30分钟；d. Add polymeric isocyanate dropwise to the mixed solution prepared in step c, and stir for 15-30 minutes;
e．将在步骤d中制备的混合液浇注到聚四氟乙烯涂层模具中，在室温下静置48小时后，在真空干燥箱中于30-40℃下干燥72小时，得到电解质膜；e. pouring the mixed solution prepared in step d into a polytetrafluoroethylene-coated mould, standing at room temperature for 48 hours, and then drying in a vacuum oven at 30-40°C for 72 hours to obtain an electrolyte membrane;
f．将在步骤e中干燥后的电解质膜，在140℃条件下高温固化至少24小时后，消除电解质膜中残留的异氰酸酯基团，最终制得厚度为20-60μm的固态电解质薄膜。f. The electrolyte membrane dried in step e is cured at 140° C. for at least 24 hours at high temperature to eliminate the residual isocyanate groups in the electrolyte membrane, and finally obtain a solid electrolyte film with a thickness of 20-60 μm.
本发明与现有技术相比较，具有如下显而易见的突出实质性特点和显著优点：Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:
1. 本发明制备的固态电解质中锂盐与水性聚合物链段之间不是简单的共混，而是形成了有效的配位体，通过配位本的络合－解络合过程实现了锂离子的迁移，锂盐影响了聚合物分子链段的规整性，降低了聚合物电解质结晶度及熔点，从而使分子链段热运动能力增强；聚合异氰酸酯的-NCO可以与水性聚合物中的羟基发生化学反应，使电解质内部形成空间网络，通过“后处理”加热则使残余的NCO基团进一步交联，改变链段排列的规整性，进一步提高链段的运动能力；而纳米无机颗粒能够降低高分子材料的结晶能力，增加无定形区含量；1. In the solid electrolyte prepared by the present invention, the lithium salt and the water-based polymer chain segment are not simply blended, but an effective ligand is formed, and the lithium salt is realized through the complexation-decomplexation process of the coordination book. The migration of ions, the lithium salt affects the regularity of the polymer molecular segment, reduces the crystallinity and melting point of the polymer electrolyte, thereby enhancing the thermal mobility of the molecular segment; A chemical reaction occurs to form a spatial network inside the electrolyte, and the residual NCO groups are further cross-linked through "post-treatment" heating, which changes the regularity of the chain segment arrangement and further improves the movement capacity of the chain segment; while nano-inorganic particles can reduce The crystallization ability of polymer materials increases the content of amorphous regions;
2. 本发明方法制得的聚合物复合材料固态电解质具有离子导电率高和力学性能优良的特点；2. The polymer composite solid electrolyte prepared by the method of the present invention has the characteristics of high ionic conductivity and excellent mechanical properties;
3. 本发明使用的方法和已有的聚合物固态电解质制备方法相比，不仅产品的性能更加优越，避免了有机溶剂的释放，且可显著降低生产成本。3. Compared with the existing polymer solid electrolyte preparation method, the method used in the present invention not only has better product performance, avoids the release of organic solvents, but also can significantly reduce production costs.
具体实施方式Detailed ways
本发明的优选实施例详述如下：Preferred embodiments of the present invention are described in detail as follows:
实施例一：Embodiment one:
在本实施例中，聚合物复合材料固态电解质的制备方法，基于水溶液浇铸法，步骤如下：In this example, the preparation method of the polymer composite solid electrolyte is based on the aqueous solution casting method, and the steps are as follows:
a．将600份冷水注入反应釜中，开动搅拌机，加入60 份醇解度88%的聚乙烯醇，缓慢升温至90℃，机械混合2小时获得均匀溶液；a. Pour 600 parts of cold water into the reaction kettle, start the mixer, add 60 parts of polyvinyl alcohol with an alcoholysis degree of 88%, slowly raise the temperature to 90°C, and mix mechanically for 2 hours to obtain a uniform solution;
b．降温至50℃，加入30份高氯酸锂，搅拌2.5小时，使其完全溶解在聚乙烯醇水溶液中；b. Cool down to 50°C, add 30 parts of lithium perchlorate, and stir for 2.5 hours to completely dissolve it in the aqueous solution of polyvinyl alcohol;
c．继续降温至40℃，将25份二氧化硅纳米粒子的水性分散液（含固量20%）缓缓加入，在超声波与机械搅拌的共同作用下，混合3小时；c. Continue to cool down to 40°C, slowly add 25 parts of an aqueous dispersion of silica nanoparticles (20% solid content), and mix for 3 hours under the joint action of ultrasonic waves and mechanical stirring;
d．滴加5份可水分散聚合异氰酸酯，并搅拌15-30分钟；d. Add 5 parts of water-dispersible polymeric isocyanate dropwise and stir for 15-30 minutes;
e．将上述溶液浇注到聚四氟乙烯涂层模具中室温静置48小时后，在真空干燥箱中40℃下干燥72小时；e. The above solution was poured into a polytetrafluoroethylene coated mold and left to stand at room temperature for 48 hours, then dried in a vacuum oven at 40°C for 72 hours;
f．将干燥后的电解质膜于140℃固化24小时，消除其中残留的-NCO，获得厚度为25μm的固态电解质薄膜。f. The dried electrolyte membrane was cured at 140° C. for 24 hours to eliminate the remaining -NCO, and a solid electrolyte film with a thickness of 25 μm was obtained.
实施例二：Embodiment two:
本实施例与实施例一基本相同，特别之处在于：This embodiment is basically the same as Embodiment 1, especially in that:
在本实施例中，聚合物复合材料固态电解质的制备方法，步骤如下：In this embodiment, the preparation method of polymer composite solid electrolyte, the steps are as follows:
a．将600份冷水注入反应釜中，开动搅拌机，加入55 份聚醋酸乙烯－乙烯乳（VAE）胶粉，缓慢升温至60℃，机械混合2小时获得均匀溶液；a. Pour 600 parts of cold water into the reaction kettle, start the mixer, add 55 parts of polyvinyl acetate-ethylene emulsion (VAE) rubber powder, slowly raise the temperature to 60°C, and mix mechanically for 2 hours to obtain a uniform solution;
b．降温至50℃，加入35份碳酸锂，搅拌3小时，使其完全溶解在VAE溶液中；b. Cool down to 50°C, add 35 parts of lithium carbonate, and stir for 3 hours to completely dissolve in the VAE solution;
c．继续降温至30-40℃，将30份纳米碳酸钙水性分散液（含固量20%）缓缓加入，在超声波与机械搅拌的共同作用下，混合2.5小时；c. Continue to cool down to 30-40°C, slowly add 30 parts of nano-calcium carbonate aqueous dispersion (with a solid content of 20%), and mix for 2.5 hours under the joint action of ultrasonic waves and mechanical stirring;
d．滴加4份可水分散聚合多异氰酸酯，并搅拌15-30分钟；d. Add 4 parts of water-dispersible polymeric polyisocyanate dropwise and stir for 15-30 minutes;
e．本步骤与实施例一相同；e. This step is identical with embodiment one;
f．将干燥后的电解质膜于140℃固化24小时，消除其中残留的-NCO，获得厚度为35μm的固态电解质薄膜。f. The dried electrolyte membrane was cured at 140°C for 24 hours to eliminate the residual -NCO, and a solid electrolyte film with a thickness of 35 μm was obtained.
实施例三：Embodiment three:
本实施例与前述实施例基本相同，特别之处在于：This embodiment is basically the same as the previous embodiment, and the special features are:
在本实施例中，聚合物复合材料固态电解质的制备方法，步骤如下：In this embodiment, the preparation method of polymer composite solid electrolyte, the steps are as follows:
a．将600份冷水注入反应釜中，开动搅拌机，加入50 份醇解度99%的聚乙烯醇和10份羧甲基纤维素，缓慢升温至95℃，机械混合2小时获得均匀溶液；a. Pour 600 parts of cold water into the reaction kettle, start the mixer, add 50 parts of polyvinyl alcohol with an alcoholysis degree of 99% and 10 parts of carboxymethyl cellulose, slowly raise the temperature to 95 ° C, and mix mechanically for 2 hours to obtain a uniform solution;
b．降温至50℃，加入30份硫酸锂，搅拌2.5小时，使其完全溶解在聚乙烯醇和羧甲基纤维素的混合水溶液中；b. Cool down to 50°C, add 30 parts of lithium sulfate, and stir for 2.5 hours to completely dissolve in the mixed aqueous solution of polyvinyl alcohol and carboxymethyl cellulose;
c．继续降温至30-40℃，将20份纳米二氧化钛水分散液（含固量20%）缓缓加入，在超声波与机械搅拌的共同作用下，混合3小时；c. Continue to cool down to 30-40°C, slowly add 20 parts of nano-titanium dioxide aqueous dispersion (with a solid content of 20%), and mix for 3 hours under the joint action of ultrasonic waves and mechanical stirring;
d．滴加6份高官能度聚合多异氰酸酯，并搅拌15-30分钟；d. Add 6 parts of high-functionality polyisocyanate dropwise and stir for 15-30 minutes;
e．本步骤与实施例一相同；e. This step is identical with embodiment one;
f．将干燥后的电解质膜于140℃固化24小时，消除其中残留的-NCO，获得厚度为30μm的固态电解质薄膜。f. The dried electrolyte membrane was cured at 140°C for 24 hours to eliminate the remaining -NCO, and a solid electrolyte film with a thickness of 30 μm was obtained.
材料性能分析测试：Material performance analysis test:
根据实施例一~实施例三所制固态电解质的主要性能进行检测，比较如下表1。The main properties of the solid electrolytes prepared in Examples 1 to 3 were tested and compared in Table 1 below.
表1. 本发明实施例固态电解质的主要物理力学性能Table 1. The main physical and mechanical properties of the solid electrolyte of the embodiments of the present invention
由表1可见，本发明的聚合物复合材料固态电解质具有良好的常温离子电导率和力学性能，更为重要的是其松弛时间较小，可确保长期稳定的服役能力。本发明利用无机纳米粒子、锂盐、多异氰酸酯改性水性聚合物制备全固体电解质，可广泛应用于锂离子二次电池工业领域。It can be seen from Table 1 that the polymer composite solid electrolyte of the present invention has good room temperature ionic conductivity and mechanical properties, and more importantly, its relaxation time is small, which can ensure long-term stable service ability. The invention uses inorganic nanoparticles, lithium salts, and polyisocyanate-modified water-based polymers to prepare all-solid electrolytes, and can be widely used in the industrial field of lithium-ion secondary batteries.
上面对本发明实施例进行了说明，但本发明不限于上述实施例，还可以根据本发明的发明创造的目的做出多种变化，凡依据本发明技术方案的精神实质和原理下做的改变、修饰、替代、组合、简化，均应为等效的置换方式，只要符合本发明的发明目的，只要不背离本发明聚合物复合材料固态电解质及其制备方法的技术原理和发明构思，都属于本发明的保护范围。The embodiments of the present invention have been described above, but the present invention is not limited to the above-mentioned embodiments, and various changes can also be made according to the purpose of the invention of the present invention. All changes made under the spirit and principles of the technical solutions of the present invention, Modification, substitution, combination, and simplification should all be equivalent replacement methods, as long as they meet the purpose of the invention, as long as they do not deviate from the technical principle and inventive concept of the polymer composite solid electrolyte and its preparation method of the invention, they all belong to this invention. protection scope of the invention.
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| CN201410745343.0ACN104600357B (en) | 2014-12-08 | 2014-12-08 | Polymer composites solid electrolyte and preparation method thereof |
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| CN201410745343.0ACN104600357B (en) | 2014-12-08 | 2014-12-08 | Polymer composites solid electrolyte and preparation method thereof |
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| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20170531 Termination date:20191208 |