CN102903524A - Electronic storage material for all solid-state electric energy storage device - Google Patents
Electronic storage material for all solid-state electric energy storage device Download PDFInfo
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Abstract
本发明涉及一种用于全固态电储能器件的电子存储材料，所述的电子存储材料为具有大共轭结构的铝、锌、镓、铟的有机金属配合物，该金属配合物的纯度≥96％。本发明的电子存储材料具有高的电子迁移率，有利于电子的迁移，提高储能器件的充放电效率及其较高的电子亲和势，有利于电子的注入与存储，提高器件的储能效率。用本发明的电子存储材料制备全固态存储器件时，可选择的正电荷存储材料多且全固态电储能器件的能量密度大，功率密度高。The invention relates to an electronic storage material used for all-solid-state electric energy storage devices. The electronic storage material is an organometallic complex of aluminum, zinc, gallium, and indium with a large conjugated structure. The purity of the metal complex is ≥96%. The electronic storage material of the present invention has high electron mobility, which is beneficial to the migration of electrons, improves the charging and discharging efficiency of energy storage devices and its high electron affinity, is beneficial to the injection and storage of electrons, and improves the energy storage of devices. efficiency. When the electronic storage material of the present invention is used to prepare an all-solid-state storage device, there are many positive charge storage materials to choose from, and the all-solid-state electric energy storage device has high energy density and high power density.
Description
发明领域field of invention
本发明涉及一种用于全固态电储能器件的电子存储材料。The invention relates to an electronic storage material used for an all-solid-state electric energy storage device.
背景技术Background technique
20世纪90年代以来，清洁能源利用的呼声日渐高涨，以保证人类能源的可持续供应，然而我国储能仍处于初级发展阶段，无法大规模的投入应用。目前能源市场迫切需要储能技术，但市场上储能技术种类繁多，每种储能技术或多或少都存在问题。如锂离子电池虽然其能量密度高、循环寿命长、自放电功率小、无记忆效应和绿色环保等，但其安全性、成本、容量等问题仍未得到解决，尤其是其功率密度较低(这主要是由于电池要通过电化学反应才能产生电荷并进行电能的存储，因此，电池的充电或放电需要一定的时间，导致其功率密度较低)。Since the 1990s, the voice of clean energy utilization has been increasing day by day to ensure the sustainable supply of human energy. However, my country's energy storage is still in the initial stage of development and cannot be put into large-scale application. At present, the energy market urgently needs energy storage technology, but there are many kinds of energy storage technologies on the market, and each energy storage technology has more or less problems. For example, although lithium-ion batteries have high energy density, long cycle life, low self-discharge power, no memory effect, and environmental protection, their safety, cost, and capacity issues have not been resolved, especially their low power density ( This is mainly due to the fact that the battery can generate charge and store electrical energy through an electrochemical reaction, therefore, it takes a certain amount of time to charge or discharge the battery, resulting in a low power density).
超级电容器是近年来发展起来的一种介于传统电容器和二次电池之间的新型储能器件，它具有比能量高，功率密度大，清洁无污染、充放电速度快、寿命长达百万次，是一种新型、实用、高效的储能器件。但是，超级电容的能量密度仍远小于锂电池，这限制了超级电容器在储能领域的应用。同时，由于仍然使用液态电解质，这种电容器同样存在电解质渗漏等安全隐患。Supercapacitor is a new type of energy storage device developed in recent years between traditional capacitors and secondary batteries. It has high specific energy, high power density, clean and pollution-free, fast charging and discharging speed, and a life span of one million Second, it is a new, practical and efficient energy storage device. However, the energy density of supercapacitors is still much smaller than that of lithium batteries, which limits the application of supercapacitors in the field of energy storage. At the same time, since liquid electrolyte is still used, this kind of capacitor also has potential safety hazards such as electrolyte leakage.
因此，开发一种既有较高的能量密度，又具有大的功率密度的全固态电储能器件对于储能具有重要的意义，有助于提高能源的利用效率，其储能器件的电子存储材料对于全固态电储能器件的功率密度、能量密度、充放电电压等有着重要的影响。Therefore, the development of an all-solid-state electric energy storage device with both high energy density and large power density is of great significance for energy storage, which helps to improve the utilization efficiency of energy, and the electronic storage of its energy storage device Materials have an important influence on the power density, energy density, charging and discharging voltage of all-solid-state electric energy storage devices.
发明内容Contents of the invention
本发明的目的是提供一种具有高的电子迁移率、高的电子亲和势、稳定性好的用于全固态电储能器件的电子存储材料。The object of the present invention is to provide an electronic storage material with high electron mobility, high electron affinity and good stability for all solid-state electric energy storage devices.
本发明的电子存储材料为具有大共轭结构的有机金属配合物。The electronic storage material of the present invention is an organometallic complex with a large conjugated structure.
所述的有机金属配合物是铝、锌、镓、铟的配合物；The organometallic complex is a complex of aluminum, zinc, gallium, indium;
优选的有机金属配合物为The preferred organometallic complexes are
中的一种；one of
其中，所述的R1为铝、镓、铟中的一种；Wherein, the R1 is one of aluminum, gallium and indium;
所述的R2为铝、镓、铟中的一种；The R2 is one of aluminum, gallium and indium;
所述的R3为铝、镓、铟中的一种；The R3 is one of aluminum, gallium and indium;
所述的R4为CH3OH、Cl中的一种；The R4 is one of CH 3 OH and Cl;
所述的金属配合物纯度≥96％；The purity of the metal complex is ≥96%;
所述的电子存储材料制备全固态电储能器件时，正电荷存储材料可以为有机硅化合物、聚对苯撑乙烯、聚乙烯咔唑、聚酚噻嗪中的一种或几种的混合物；When the electronic storage material is used to prepare an all-solid-state electric energy storage device, the positive charge storage material can be one or a mixture of organosilicon compounds, poly(p-phenylene vinylene), polyvinylcarbazole, and polyphenothiazine;
所述的电子存储材料制备全固态电储能器件时，可以用真空蒸镀、湿法、蒸气喷印、气相沉积、丝网印刷、喷墨打印的方法制备成电子存储材料薄膜，薄膜的厚度为100nm～10μm；When preparing an all-solid-state electric energy storage device from the electronic storage material, it can be prepared into an electronic storage material film by vacuum evaporation, wet method, steam jet printing, vapor deposition, screen printing, and inkjet printing. The thickness of the film is 100nm ~ 10μm;
所述的电子存储材料制备全固态电储能器件时，电极为金属银或其合金、金属铝或其合金、金属铝包覆氧化铝薄膜中一种；When the electronic storage material is used to prepare an all-solid-state electric energy storage device, the electrode is one of metallic silver or its alloy, metallic aluminum or its alloy, and metallic aluminum-coated aluminum oxide film;
所述的电子存储材料制备全固态电储能器件时，绝缘材料为有机聚合物/高介电常数物质的混合物；When the electronic storage material is used to prepare an all-solid-state electric energy storage device, the insulating material is a mixture of organic polymer/high dielectric constant material;
其中，所述的有机聚合物为聚酰亚胺、聚酯、聚四氟乙烯中的一种；Wherein, the organic polymer is one of polyimide, polyester and polytetrafluoroethylene;
所述的高介电常数物质为钨酸铅、钛酸钡中的一种。The high dielectric constant material is one of lead tungstate and barium titanate.
本发明的用于全固态电储能器件的电子存储材料具有如下优点：The electronic storage material used for all-solid-state electric energy storage devices of the present invention has the following advantages:
(1)本发明的电子存储材料具有较高的电子亲和势，有利于电子的注入与存储，提高器件的储能效率；(1) The electron storage material of the present invention has higher electron affinity, is conducive to the injection and storage of electrons, and improves the energy storage efficiency of the device;
(2)本发明的电子存储材料具有高的电子迁移率，有利于电子的迁移，提高储能器件的充放电效率；(2) The electronic storage material of the present invention has high electron mobility, which is conducive to the migration of electrons and improves the charge and discharge efficiency of energy storage devices;
(3)用本发明的电子存储材料制备全固态电储能器件时，可选择的正电荷存储材料种类多且全固态电储能器件的能量密度大，功率密度高。(3) When using the electronic storage material of the present invention to prepare all-solid-state electric energy storage devices, there are many types of positive charge storage materials that can be selected, and the all-solid-state electric energy storage devices have high energy density and high power density.
具体实施方式Detailed ways
实施例1Example 1
选择纯度为96％的三(8-羟基喹啉)铝为电子存储材料，聚乙烯咔唑聚合物(平均分子量为1930)为正电荷存储材料，聚酰亚胺/钨酸铅混合物(质量比4∶1)为复合绝缘材料，金属银为电极材料，采用真空蒸镀的方法制备有机薄膜。采用真空蒸镀技术在金属银表面制备一层面积为10×10cm2，厚度为10μm的三(8-羟基喹啉)铝，然后在三(8-羟基喹啉)铝表面旋涂一层厚度为5μm的聚酰亚胺/钨酸铅复合绝缘材料。最后在绝缘材料表面旋涂一层厚度为6μm的聚乙烯咔唑聚合物(平均分子量为1930)。干燥固化后，在聚合物表面真空蒸镀一层100nm厚的金属银，即得到全固态电储能器件。测试表明，该全固态电储能器件在2min内完成充电，能量密度为514Wh/kg，功率密度为8.2kW/kg。Selecting three (8-hydroxyquinoline) aluminums with a purity of 96% is an electronic storage material, polyvinylcarbazole polymer (average molecular weight is 1930) is a positive charge storage material, polyimide/lead tungstate mixture (mass ratio 4:1) is a composite insulating material, metallic silver is an electrode material, and an organic thin film is prepared by vacuum evaporation. Prepare a layer of tris(8-hydroxyquinoline)aluminum with an area of 10×10cm 2 and a thickness of 10μm on the surface of metal silver by vacuum evaporation technology, and then spin-coat a layer of tris(8-hydroxyquinoline)aluminum on the surface of tris(8-hydroxyquinoline)aluminum 5μm polyimide/lead tungstate composite insulating material. Finally, spin-coat a layer of polyvinylcarbazole polymer (average molecular weight: 1930) with a thickness of 6 μm on the surface of the insulating material. After drying and solidification, a layer of metallic silver with a thickness of 100 nm is vacuum evaporated on the surface of the polymer to obtain an all-solid-state electric energy storage device. Tests show that the all-solid-state electric energy storage device can be charged within 2 minutes, with an energy density of 514Wh/kg and a power density of 8.2kW/kg.
实施例2Example 2
选择纯度为96.8％的三(5-羟甲基-8-羟基喹啉)铝为电子存储材料，聚甲基苯基硅烷9，10-共蒽聚合物(平均分子量为2522)为正电荷存储材料，聚酯/钛酸钡混合物(质量比3∶2)为复合绝缘材料，金属铝为电极材料。采用真空蒸镀技术在玻璃表面依次蒸镀面积为10×10cm2，厚度为100nm的金属铝电极，厚度为100nm的三(5-羟甲基-8-羟基喹啉)铝，厚度为200nm的聚酯/钛酸钡复合绝缘材料。然后在表面用4000rpm的转速旋涂质量浓度为5‰的聚甲基苯基硅烷9，10-共蒽聚合物的甲苯溶液，干燥固化后，在聚合物表面真空蒸镀一层厚度为100nm的金属铝，即得到全固态电储能器件。测试表明，该全固态电储能器件在1.5min内完成充电，能量密度为467Wh/kg，功率密度为8.6kW/kg。Three (5-hydroxymethyl-8-hydroxyquinoline) aluminum with a purity of 96.8% is selected as an electronic storage material, and polymethylphenylsilane 9,10-coanthracene polymer (average molecular weight is 2522) is a positive charge storage material. Materials, polyester/barium titanate mixture (mass ratio 3:2) is a composite insulating material, and metal aluminum is an electrode material. Vacuum evaporation technology is used to vapor-deposit metal aluminum electrodes with an area of 10×10cm 2 and a thickness of 100nm on the glass surface, tris(5-hydroxymethyl-8-hydroxyquinoline)aluminum with a thickness of 100nm, and an electrode with a thickness of 200nm. Polyester/barium titanate composite insulation. Then spin-coat the toluene solution of polymethylphenylsilane 9,10-coanthracene polymer with a mass concentration of 5‰ on the surface at a speed of 4000rpm. After drying and curing, vacuum evaporate a layer of 100nm thick on the surface of the polymer. Metal aluminum, that is, to obtain an all-solid-state electric energy storage device. Tests show that the all-solid-state electric energy storage device can be charged within 1.5 minutes, with an energy density of 467Wh/kg and a power density of 8.6kW/kg.
实施例3Example 3
选择纯度为97.2％的二〔1-苯基-2-(2-羟基苯基)苯并咪唑〕锌为电子存储材料，聚对苯撑乙烯(平均分子量为8050)为正电荷存储材料，聚四氟乙烯/钛酸钡混合物(质量比9∶1)为复合绝缘材料，金属铝包覆氧化铝薄膜为电极材料，采用真空蒸镀的方法制备有机薄膜。采用真空蒸镀技术在电极表面制备一层面积为10×10cm2，厚度为1μm的二〔1-苯基-2-(2-羟基苯基)苯并咪唑〕锌，然后在电子存储材料层表面旋涂一层厚度为5μm的聚四氟乙烯/钛酸钡混合物。最后在绝缘材料层表面旋涂一层厚度为2μm的聚对苯撑乙烯。干燥固化后，在聚合物表面真空蒸镀一层100nm厚的电极，即得到本发明所述的全固态电储能器件。测试表明，该全固态电储能器件在3min内完成充电，能量密度为402Wh/kg，功率密度为9.2kW/kg。Two [1-phenyl-2-(2-hydroxyphenyl) benzimidazole] zinc with a purity of 97.2% is selected as the electronic storage material, and poly(p-phenylene vinylene) (the average molecular weight is 8050) is the positive charge storage material. Tetrafluoroethylene/barium titanate mixture (mass ratio 9:1) is a composite insulating material, aluminum oxide film coated with metal aluminum is an electrode material, and an organic film is prepared by vacuum evaporation. A layer of bis[1-phenyl-2-(2-hydroxyphenyl)benzimidazole]zinc with an area of 10×10cm 2 and a thickness of 1 μm was prepared on the surface of the electrode by vacuum evaporation technology, and then deposited on the electronic storage material layer Spin-coat a layer of polytetrafluoroethylene/barium titanate mixture with a thickness of 5 μm on the surface. Finally, a layer of poly(p-phenylene vinylene) with a thickness of 2 μm was spin-coated on the surface of the insulating material layer. After drying and curing, a layer of 100 nm-thick electrode is vacuum-evaporated on the surface of the polymer to obtain the all-solid-state electric energy storage device of the present invention. Tests show that the all-solid-state electric energy storage device can be charged within 3 minutes, with an energy density of 402Wh/kg and a power density of 9.2kW/kg.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1479930A (en) * | 2000-12-06 | 2004-03-03 | ���տ�˹�ɷ�����˾ | double layer capacitor |
| CN101043069A (en) * | 2006-03-21 | 2007-09-26 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic device |
| CN101134814A (en) * | 2006-08-24 | 2008-03-05 | E.I.内穆尔杜邦公司 | hole transport polymer |
| WO2012021289A1 (en) * | 2010-08-12 | 2012-02-16 | Massachusetts Institute Of Technology | Flexible conducting polymer energy storage device |
-
2012
- 2012-10-18 CN CN2012103955439A patent/CN102903524A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1479930A (en) * | 2000-12-06 | 2004-03-03 | ���տ�˹�ɷ�����˾ | double layer capacitor |
| CN101043069A (en) * | 2006-03-21 | 2007-09-26 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic device |
| CN101134814A (en) * | 2006-08-24 | 2008-03-05 | E.I.内穆尔杜邦公司 | hole transport polymer |
| WO2012021289A1 (en) * | 2010-08-12 | 2012-02-16 | Massachusetts Institute Of Technology | Flexible conducting polymer energy storage device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106645925A (en) * | 2016-09-11 | 2017-05-10 | 浙江大学 | Electric energy storage device power test system |
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