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WO2023109408A1 - Electric double layer capacitor - Google Patents

Electric double layer capacitor Download PDF

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Publication number
WO2023109408A1
WO2023109408A1 PCT/CN2022/131965 CN2022131965W WO2023109408A1 WO 2023109408 A1 WO2023109408 A1 WO 2023109408A1 CN 2022131965 W CN2022131965 W CN 2022131965W WO 2023109408 A1 WO2023109408 A1 WO 2023109408A1
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WO
WIPO (PCT)
Prior art keywords
porous carbon
electric double
layer capacitor
double layer
electrolyte
Prior art date
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PCT/CN2022/131965
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French (fr)
Chinese (zh)
Inventor
袁峻
荆葛
谢双
张力
于学文
乔志军
Original Assignee
宁波中车新能源科技有限公司
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Publication of WO2023109408A1 publication Critical patent/WO2023109408A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the technical field of capacitors, in particular to an electric double layer capacitor.
  • Electric double layer capacitor also known as super capacitor
  • Electric double layer capacitor is one of the most popular high-power energy storage devices on the market at present. It is an energy storage device based on the principle of electric double layer energy storage. It has the advantages of long working temperature and wide operating temperature range, but also has the disadvantages of relatively low energy density.
  • the most mature product on the market is 2.7V3000F, with an energy density of about 5.6Wh/kg.
  • With the gradual stabilization of high-voltage electrolyte and high-voltage activated carbon new products that have been promoted in the past three years include 2.85V3000F products and 3.0V3000F product, energy density increased to 7.5Wh/kg.
  • the volume capacity C of the capacitor is mainly determined by the specific surface area, pore size, electrolyte salt size and charge number of the activated carbon. According to the size of the positive and negative ions of the current commercial electrolyte salt, the size of the anion is the limit of the stable state, and the size of the cation has little room for improvement on the basis of the existing SBP and DMP salts, so that according to the existing electrolyte Salt does not increase capacitor capacity any further.
  • the invention provides an electric double layer capacitor with high capacity and high energy density.
  • an electric double layer capacitor the capacitor includes a multivalent ion electrolyte, a positive porous carbon electrode, a negative porous carbon electrode, a diaphragm, a positive porous carbon electrode, a negative porous carbon electrode
  • the pore size of the mesoporous carbon is 3-6 times that of the ion particle size in the multivalent ion electrolyte;
  • the multivalent ion electrolyte includes the following raw materials in mass percentage: 10-35%wt electrolyte salt, 65-90%wt electrolytic liquid solvent.
  • the pore diameters of the porous carbon electrodes in the positive electrode and the negative electrode porous carbon electrodes are both 4-5 times of the particle diameters of the ions in the polyvalent ion electrolyte.
  • the ions actually exist in the form of solvated ions, and the actual size is about 1.5-2 times the theoretical size of the ion.
  • the present invention controls the porous carbon pore size to be 4-5 times the particle size of the ion in the polyvalent ion electrolyte, which can Avoid the negative impact that the porous carbon pore size is too small to cause adsorption and the capacitor resistance increases, but when the porous carbon pore size is too large, the material density and the total number of pore sizes decrease, resulting in a negative impact on the final capacitor capacity.
  • the capacity ratio of the positive porous carbon electrode to the negative porous carbon electrode is (1-1.5):1.
  • the present invention controls the capacity ratio of positive and negative porous carbon electrodes at (1-1.5): 1, which can increase the life of the capacitor under high voltage, and controls the content of electrolyte salt at 10-35%, because it is affected by the electrolyte
  • the solubility of the salt affects the content and cannot be further improved. When the content exceeds 35%, the electrolyte salt solubility reaches the limit, resulting in the inability to complete the injection.
  • the salt content of the electrolyte is lower than 10%, the internal resistance of the capacitor at low temperature is high or even the capacity is insufficient.
  • the positive and negative porous carbon electrodes also include a binder, a conductive agent, a dispersant, and a current collector, wherein the binder includes one or more of SBR, CMC, PTFE, and PVDF, and the conductive agent includes conductive carbon black, scientific One or more of carbon, graphene, and carbon nanotubes, and the current collector includes carbon-coated aluminum foil, aluminum foil, aluminum foil with holes, copper foil, and copper foil with holes.
  • the separator used in the electric double-layer capacitor of the present invention is a cellulose paper separator, a polyolefin separator, a coating-treated polyester film, a polyimide film, a polyamide film, spandex or aramid fiber film, and a non-woven fabric separator. kind of.
  • the electrolytic solution salt includes monovalent anions and divalent cations.
  • the monovalent anion is one or more of BF 4 - , PF 6 - , TFSI - .
  • the divalent cation is one or more of nitrogen-containing heterocyclic imidazole, thiazole, pyrazole, and pyrimidine.
  • the divalent cations are dimethylpyrimidine and dimethylimidazole.
  • the electrolyte solvent is one of acetonitrile (AN), polycarbonate (PC) and ionic liquid.
  • the number of charges carried by the positive and negative ions in the polyvalent ion electrolyte is greater than one.
  • the porous carbon in the positive porous carbon electrode has a pore diameter of 0.8-1.5 nm.
  • the porous carbon in the negative electrode porous carbon electrode has a pore diameter of 2-3.0 nm.
  • the porous carbon in the positive and negative porous carbon electrodes includes one of activated carbon, mesoporous carbon, carbon aerogel, carbon fiber, carbon nanotube, carbon black, hard carbon, and graphene. or more.
  • the porous carbon in the positive porous carbon electrode is petroleum coke-activated activated carbon or carbon aerogel.
  • the porous carbon in the negative porous carbon electrode is carbon aerogel or activated carbon activated by coconut shell water vapor.
  • the capacity is 5000-6000F, and the energy density is 12-15Wh/kg.
  • the present invention Compared with the prior art, the present invention has the following beneficial effects: the present invention optimizes the charge and ion content of anions and cations in the electrolyte, and controls the porous carbon pore size and multivalent ions in the positive porous carbon electrode and the negative porous carbon electrode.
  • the ion particle size in the electrolyte is matched to achieve the best aperture ratio, so that the single capacity of the electric double layer capacitor can reach up to 5400-6000F, and the energy density can reach up to 12.5-14.7Wh/kg;
  • the optimization also improves the withstand voltage performance of the capacitor to a certain extent.
  • Example 1 The difference from Example 1 is only that the pore diameter of the petroleum coke-activated activated carbon is about 1.8nm.
  • Example 1 The difference from Example 1 is only that the pore diameter of the petroleum coke-activated activated carbon is about 0.5nm.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • Example 1 The difference with Example 1 is only that the pore diameter of the activated carbon activated by coconut shell water vapor is about 3.3nm.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • Example 1 The difference with Example 1 is only that the pore diameter of the activated carbon activated by coconut shell water vapor is about 1.8nm.
  • Example 1 The only difference from Example 1 is that the electrolytic solution includes the following raw materials in mass percentage: 25% ammonium tetraethyl tetrafluoroborate, 75% acetonitrile.
  • Example 1 The only difference from Example 1 is that the electrolyte is the following raw materials in mass percentage: 5% dimethyl pyrimidine tetrafluoroborate, 95% acetonitrile.
  • Example 1 The only difference from Example 1 is that the electrolyte solution is made of the following raw materials in mass percentage: 40% dimethylpyrimidine tetrafluoroborate, 60% polycarbonate.
  • Example 1 The difference with Example 1 is only that the pore diameter of the activated carbon activated by coconut shell water vapor is about 1.5nm.
  • Example 1 The difference with Example 1 is only that the pore diameter of the petroleum coke-activated activated carbon is about 2.5nm.
  • Table 1 Physical performance testing results of electric double layer capacitors prepared in Examples 1-7 and Comparative Examples 1-5
  • test method of DC life capacity retention rate is rated voltage/65°C float charge for 500h; the test method of cycle life capacity retention rate is the capacity after 50,000 cycles of rated voltage to half voltage 100A.
  • the present invention adjusts the pore size of the porous carbon in the positive and negative porous carbon electrodes correspondingly by optimizing the content of anions and cations in the electrolyte, thereby improving the monomer capacity and energy density of the electric double layer capacitor, and at the same time
  • the optimization of the composition content of the electrolyte in the present invention also improves the withstand voltage performance of the capacitor to a certain extent.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

Particularly disclosed is an electric double layer capacitor, which belongs to the technical field of capacitors. The charge amounts of anions and cations and the content of ions in an electrolyte are optimized, and the aperture of porous carbon in a positive porous carbon electrode and a negative porous carbon electrode is controlled to match the particle size of ions in a multivalent ion electrolyte to reach the optimal aperture ratio, such that the capacity of an electric double layer capacitor unit can reach 5400-6000 F at most, and the energy density thereof can reach 12.5-14.7 Wh/kg at most; moreover, by means of the optimization of the content of components in the electrolyte, the voltage resistance performance of the capacitor is also improved to a certain extent.

Description

一种双电层电容器An electric double layer capacitor 技术领域technical field
本发明属于电容器技术领域，具体涉及一种双电层电容器。The invention belongs to the technical field of capacitors, in particular to an electric double layer capacitor.
背景技术Background technique
双电层电容器(又称超级电容器)是目前市场上最为热门的高功率储能器件之一，是基于双电层储能原理的储能器件，具有功率密度高、充放电时间短、循环寿命长、工作温度范围宽等优点，同时也具有能量密度相对较低等劣势。目前市场上最为成熟的产品是2.7V3000F，能量密度约为5.6Wh/kg，而随着高耐压电解液和高耐压活性炭的逐步稳定，近三年开始推广的新产品包含2.85V3000F产品和3.0V3000F产品，能量密度提升至7.5Wh/kg。Electric double layer capacitor (also known as super capacitor) is one of the most popular high-power energy storage devices on the market at present. It is an energy storage device based on the principle of electric double layer energy storage. It has the advantages of long working temperature and wide operating temperature range, but also has the disadvantages of relatively low energy density. At present, the most mature product on the market is 2.7V3000F, with an energy density of about 5.6Wh/kg. With the gradual stabilization of high-voltage electrolyte and high-voltage activated carbon, new products that have been promoted in the past three years include 2.85V3000F products and 3.0V3000F product, energy density increased to 7.5Wh/kg.
基于超级电容器的能量公式(E＝0.5CV 2)，相关工作主要围绕在如何提升体积容量C和单体的耐电压能力V上。基于目前的商业化解决方案，在保证一定寿命的基础上，采用高压实电极技术(干法和高固湿法)以及高容量活性炭能将单体容量提升至4000-4200F左右。 Based on the energy formula of the supercapacitor (E=0.5CV 2 ), related work mainly focuses on how to improve the volumetric capacity C and the withstand voltage capability V of the monomer. Based on the current commercial solutions, on the basis of ensuring a certain life, the use of high-pressure compaction electrode technology (dry method and high-solid-wet method) and high-capacity activated carbon can increase the monomer capacity to about 4000-4200F.
电容器的体积容量C主要由活性炭的比表面积、孔径以及电解液盐尺寸和电荷数决定。根据目前商业化电解液盐的正负离子尺寸，目前阴离子的尺寸已为稳定状态的极限，而阳离子的尺寸在现有SBP和DMP盐基础上可提升的空间也不大，使得根据现有电解液盐不能进一步提升电容器容量。The volume capacity C of the capacitor is mainly determined by the specific surface area, pore size, electrolyte salt size and charge number of the activated carbon. According to the size of the positive and negative ions of the current commercial electrolyte salt, the size of the anion is the limit of the stable state, and the size of the cation has little room for improvement on the basis of the existing SBP and DMP salts, so that according to the existing electrolyte Salt does not increase capacitor capacity any further.
发明内容Contents of the invention
针对现有技术中存在的不足，本发明提供了一种高容量和高能量密度的双电层电容器。Aiming at the deficiencies in the prior art, the invention provides an electric double layer capacitor with high capacity and high energy density.
为了实现上述目的，本发明采用以下技术方案：一种双电层 电容器，所述电容器包括多价离子电解液、正极多孔碳电极、负极多孔碳电极、隔膜，正极多孔碳电极、负极多孔碳电极中多孔炭孔径均为多价离子电解液中离子粒径的3-6倍；多价离子电解液包括如下质量百分比的原料：10-35％wt的电解液盐、65-90％wt的电解液溶剂。In order to achieve the above object, the present invention adopts the following technical solutions: an electric double layer capacitor, the capacitor includes a multivalent ion electrolyte, a positive porous carbon electrode, a negative porous carbon electrode, a diaphragm, a positive porous carbon electrode, a negative porous carbon electrode The pore size of the mesoporous carbon is 3-6 times that of the ion particle size in the multivalent ion electrolyte; the multivalent ion electrolyte includes the following raw materials in mass percentage: 10-35%wt electrolyte salt, 65-90%wt electrolytic liquid solvent.
在上述的一种双电层电容器中，正极多孔碳电极、负极多孔碳电极中多孔炭孔径均为多价离子电解液中离子粒径的4-5倍。In the above electric double layer capacitor, the pore diameters of the porous carbon electrodes in the positive electrode and the negative electrode porous carbon electrodes are both 4-5 times of the particle diameters of the ions in the polyvalent ion electrolyte.
在溶液中离子实际是以溶剂化离子的形式存在，实际尺寸约为离子理论尺寸的1.5-2倍，本发明控制多孔炭孔径为多价离子电解液中离子粒径的4-5倍，可以避免多孔炭孔径过小造成无法吸附导致电容器电阻变大，但是当多孔炭孔径过大则会造成材料密度下降和孔径总数下降导致最终电容器容量下降的负面影响。In the solution, the ions actually exist in the form of solvated ions, and the actual size is about 1.5-2 times the theoretical size of the ion. The present invention controls the porous carbon pore size to be 4-5 times the particle size of the ion in the polyvalent ion electrolyte, which can Avoid the negative impact that the porous carbon pore size is too small to cause adsorption and the capacitor resistance increases, but when the porous carbon pore size is too large, the material density and the total number of pore sizes decrease, resulting in a negative impact on the final capacitor capacity.
在上述的一种双电层电容器中，正极多孔碳电极与负极多孔碳电极的容量比为(1-1.5)：1。本发明将正负极多孔碳电极容量比控制在(1-1.5)：1，可以提高电容器在高电压下的寿命，并将电解液盐的含量控制在10-35％，是因为受电解液盐的溶解度影响含量无法进一步提升，当含量超过35％时由于电解液盐溶解度达到极限，导致无法完成注液。而且当电解液盐含量低于10％时也会导致低温下电容器内阻较高甚至容量不足的现象。In the above electric double layer capacitor, the capacity ratio of the positive porous carbon electrode to the negative porous carbon electrode is (1-1.5):1. The present invention controls the capacity ratio of positive and negative porous carbon electrodes at (1-1.5): 1, which can increase the life of the capacitor under high voltage, and controls the content of electrolyte salt at 10-35%, because it is affected by the electrolyte The solubility of the salt affects the content and cannot be further improved. When the content exceeds 35%, the electrolyte salt solubility reaches the limit, resulting in the inability to complete the injection. Moreover, when the salt content of the electrolyte is lower than 10%, the internal resistance of the capacitor at low temperature is high or even the capacity is insufficient.
本发明中正负极多孔碳电极还包括粘结剂、导电剂、分散剂和集流体，其中粘结剂包括SBR、CMC、PTFE、PVDF中的一种或者多种，导电剂包括导电炭黑、科琴炭、石墨烯、碳纳米管中的一种或者多种，集流体包括涂炭铝箔、铝箔、带孔铝箔、铜箔、带孔铜箔。In the present invention, the positive and negative porous carbon electrodes also include a binder, a conductive agent, a dispersant, and a current collector, wherein the binder includes one or more of SBR, CMC, PTFE, and PVDF, and the conductive agent includes conductive carbon black, scientific One or more of carbon, graphene, and carbon nanotubes, and the current collector includes carbon-coated aluminum foil, aluminum foil, aluminum foil with holes, copper foil, and copper foil with holes.
本发明双电层电容器中采用的隔膜为纤维素纸隔膜、聚烯烃类隔膜、涂层处理的聚酯膜、聚酰亚胺膜、聚酰胺膜、氨纶或芳纶膜、无纺布隔膜中的一种。The separator used in the electric double-layer capacitor of the present invention is a cellulose paper separator, a polyolefin separator, a coating-treated polyester film, a polyimide film, a polyamide film, spandex or aramid fiber film, and a non-woven fabric separator. kind of.
在上述的一种双电层电容器中，电解液盐包括一价阴离子和 二价阳离子。In an electric double layer capacitor as described above, the electrolytic solution salt includes monovalent anions and divalent cations.
在上述的一种双电层电容器中，一价阴离子为BF 4 -、PF 6 -、TFSI -中的一种或多种。 In the above electric double layer capacitor, the monovalent anion is one or more of BF 4 - , PF 6 - , TFSI - .
在上述的一种双电层电容器中，二价阳离子为含氮杂环的咪唑、噻唑、吡唑、嘧啶中的一种或多种。In the above electric double layer capacitor, the divalent cation is one or more of nitrogen-containing heterocyclic imidazole, thiazole, pyrazole, and pyrimidine.
作为优选，二价阳离子为二甲基嘧啶、二甲基咪唑。Preferably, the divalent cations are dimethylpyrimidine and dimethylimidazole.
在上述的一种双电层电容器中，电解液溶剂为乙腈(AN)、聚碳酸酯(PC)、离子液体中的一种。In the above electric double layer capacitor, the electrolyte solvent is one of acetonitrile (AN), polycarbonate (PC) and ionic liquid.
在上述的一种双电层电容器中，多价离子电解液中正负离子所带电荷数大于1。In the above electric double layer capacitor, the number of charges carried by the positive and negative ions in the polyvalent ion electrolyte is greater than one.
在上述的一种双电层电容器中，正极多孔碳电极中多孔炭孔径为0.8-1.5nm。In the above electric double layer capacitor, the porous carbon in the positive porous carbon electrode has a pore diameter of 0.8-1.5 nm.
在上述的一种双电层电容器中，负极极多孔碳电极中多孔炭孔径为2-3.0nm。In the above electric double layer capacitor, the porous carbon in the negative electrode porous carbon electrode has a pore diameter of 2-3.0 nm.
在上述的一种双电层电容器中，正负极多孔碳电极中多孔碳包括活性炭、介孔碳、碳气凝胶、碳纤维、碳纳米管、炭黑、硬炭、石墨烯中的一种或多种。In the above electric double layer capacitor, the porous carbon in the positive and negative porous carbon electrodes includes one of activated carbon, mesoporous carbon, carbon aerogel, carbon fiber, carbon nanotube, carbon black, hard carbon, and graphene. or more.
作为优选，正极多孔碳电极中多孔炭为石油焦碱活化的活性炭、碳气凝胶。Preferably, the porous carbon in the positive porous carbon electrode is petroleum coke-activated activated carbon or carbon aerogel.
作为优选，负极多孔碳电极中多孔炭为碳气凝胶或椰壳水蒸气活化的活性炭。Preferably, the porous carbon in the negative porous carbon electrode is carbon aerogel or activated carbon activated by coconut shell water vapor.
在上述的一种双电层电容器中，容量为5000-6000F，能量密度为12-15Wh/kg。In the above electric double layer capacitor, the capacity is 5000-6000F, and the energy density is 12-15Wh/kg.
与现有技术相比，本发明具有如下有益效果：本发明通过对电解液中阴阳离子电荷量、离子含量的优化，并控制正极多孔碳电极、负极多孔碳电极中多孔炭孔径与多价离子电解液中离子粒径进行匹配达到最佳孔径比，使得双电层电容器的单体容量最高可达5400-6000F、能量密度最高可达12.5-14.7Wh/kg；同时本 发明对电解液成分含量的优化一定程度上也提高了电容器的耐电压性能。Compared with the prior art, the present invention has the following beneficial effects: the present invention optimizes the charge and ion content of anions and cations in the electrolyte, and controls the porous carbon pore size and multivalent ions in the positive porous carbon electrode and the negative porous carbon electrode. The ion particle size in the electrolyte is matched to achieve the best aperture ratio, so that the single capacity of the electric double layer capacitor can reach up to 5400-6000F, and the energy density can reach up to 12.5-14.7Wh/kg; The optimization also improves the withstand voltage performance of the capacitor to a certain extent.
具体实施方式Detailed ways
以下是通过具体实施例，对本发明的技术方案作进一步的描述，但本发明并不仅限于这些实施例。The following is a further description of the technical solutions of the present invention through specific examples, but the present invention is not limited to these examples.
实施例1Example 1
S1、将孔径约1nm的石油焦碱活化活性炭、导电炭黑、CMC、SBR按照90:5:2:3的质量比混合制成正极浆料，涂覆于20μm的腐蚀铝箔，碾压后得到270μm的正极电极，其中涂炭层宽度114mm，留白11mm。S1. Mix petroleum coke-activated activated carbon with a pore size of about 1nm, conductive carbon black, CMC, and SBR in a mass ratio of 90:5:2:3 to make a positive electrode slurry, coat it on a 20μm corroded aluminum foil, and roll it to obtain 270μm positive electrode, the width of the carbon coating layer is 114mm, and the blank is 11mm.
S2、将孔径约2nm的椰壳水蒸气活化活性炭、导电炭黑、CMC、SBR按照88:7:2:3的质量比混合制成负极浆料，涂覆于20μm的腐蚀铝箔，碾压后得到220μm的负极电极，其中涂炭层宽度114mm，留白11mm。S2. Mix coconut shell water vapor-activated activated carbon with a pore size of about 2nm, conductive carbon black, CMC, and SBR in a mass ratio of 88:7:2:3 to make a negative electrode slurry, and coat it on a 20 μm corroded aluminum foil. After rolling A 220 μm negative electrode was obtained, in which the carbon-coated layer had a width of 114 mm and a blank space of 11 mm.
S3、用25μm的隔膜进行绕卷，卷绕长度为4.4m，将卷绕后的电芯进行装配干燥，并注入200g的电解液，电解液为如下质量百分比的原料：25％二甲基嘧啶四氟硼酸盐，75％乙腈。S3. Use a 25 μm diaphragm for winding, the winding length is 4.4m, assemble and dry the wound cell, and inject 200g of electrolyte, the electrolyte is the following raw materials in mass percentage: 25% dimethylpyrimidine Tetrafluoroborate, 75% acetonitrile.
实施例2：Example 2:
S1、将孔径约0.5nm的石油焦碱活化活性炭、导电炭黑、CMC、SBR按照90:5:2:3的质量比混合制成正极浆料，涂覆于20μm的腐蚀铝箔，碾压后得到270μm的正极电极，其中涂炭层宽度114mm，留白11mm。S1. Mix petroleum coke-activated activated carbon with a pore size of about 0.5nm, conductive carbon black, CMC, and SBR in a mass ratio of 90:5:2:3 to make a positive electrode slurry, and coat it on a 20μm corroded aluminum foil. After rolling A 270 μm positive electrode was obtained, in which the carbon-coated layer had a width of 114 mm and a blank space of 11 mm.
S2、将孔径约2nm的椰壳水蒸气活化活性炭、导电炭黑、CMC、SBR按照88:7:2:3的质量比混合制成负极浆料，涂覆于20μm的腐蚀铝箔，碾压后得到220μm的负极电极，其中涂炭层宽度114mm，留白11mm。S2. Mix coconut shell water vapor-activated activated carbon with a pore size of about 2nm, conductive carbon black, CMC, and SBR in a mass ratio of 88:7:2:3 to make a negative electrode slurry, and coat it on a 20 μm corroded aluminum foil. After rolling A 220 μm negative electrode was obtained, in which the carbon-coated layer had a width of 114 mm and a blank space of 11 mm.
S3、用25μm的隔膜进行绕卷，卷绕长度为4.4m，将卷绕后 的电芯进行装配干燥，并注入200g的电解液，电解液为如下质量百分比的原料：20％二甲基嘧啶四氟硼酸盐，80％乙腈。S3. Use a 25 μm diaphragm for winding, the winding length is 4.4m, assemble and dry the wound cell, and inject 200g of electrolyte, the electrolyte is the following raw materials in mass percentage: 20% dimethylpyrimidine Tetrafluoroborate, 80% acetonitrile.
实施例3：Example 3:
S1、将孔径约1.5nm的石油焦碱活化活性炭、导电炭黑、CMC、SBR按照90:5:2:3的质量比混合制成正极浆料，涂覆于20μm的腐蚀铝箔，碾压后得到270μm的正极电极，其中涂炭层宽度114mm，留白11mm。S1. Mix petroleum coke-activated activated carbon with a pore size of about 1.5nm, conductive carbon black, CMC, and SBR in a mass ratio of 90:5:2:3 to make a positive electrode slurry, and coat it on a 20μm corroded aluminum foil. After rolling A 270 μm positive electrode was obtained, in which the carbon-coated layer had a width of 114 mm and a blank space of 11 mm.
S2、将孔径约3nm的椰壳水蒸气活化活性炭、导电炭黑、CMC、SBR按照88:7:2:3的质量比混合制成负极浆料，涂覆于20μm的腐蚀铝箔，碾压后得到220μm的负极电极，其中涂炭层宽度114mm，留白11mm。S2. Mix activated carbon activated by coconut shell water vapor with a pore size of about 3nm, conductive carbon black, CMC, and SBR according to the mass ratio of 88:7:2:3 to make a negative electrode slurry, and coat it on a 20 μm corroded aluminum foil. After rolling A 220 μm negative electrode was obtained, in which the carbon-coated layer had a width of 114 mm and a blank space of 11 mm.
S3、用25μm的隔膜进行绕卷，卷绕长度为4.4m，将卷绕后的电芯进行装配干燥，并注入200g的电解液，电解液为如下质量百分比的原料：30％二甲基嘧啶四氟硼酸盐，70％乙腈。S3. Use a 25 μm diaphragm for winding, the winding length is 4.4m, assemble and dry the wound cell, and inject 200g of electrolyte, the electrolyte is the following raw materials in mass percentage: 30% dimethylpyrimidine Tetrafluoroborate, 70% acetonitrile.
实施例4：Example 4:
与实施例1的区别，仅在于，石油焦碱活化活性炭的孔径约1.8nm。The difference from Example 1 is only that the pore diameter of the petroleum coke-activated activated carbon is about 1.8nm.
实施例5：Example 5:
与实施例1的区别，仅在于，石油焦碱活化活性炭的孔径约0.5nm。The difference from Example 1 is only that the pore diameter of the petroleum coke-activated activated carbon is about 0.5nm.
实施例6:Embodiment 6:
与实施例1的区别，仅在于，椰壳水蒸气活化活性炭的孔径约3.3nm。The difference with Example 1 is only that the pore diameter of the activated carbon activated by coconut shell water vapor is about 3.3nm.
实施例7：Embodiment 7:
与实施例1的区别，仅在于，椰壳水蒸气活化活性炭的孔径约1.8nm。The difference with Example 1 is only that the pore diameter of the activated carbon activated by coconut shell water vapor is about 1.8nm.
对比例1：Comparative example 1:
与实施例1的区别，仅在于，电解液包括如下质量百分比的 原料：25％四乙基四氟硼酸铵盐，75％乙腈。The only difference from Example 1 is that the electrolytic solution includes the following raw materials in mass percentage: 25% ammonium tetraethyl tetrafluoroborate, 75% acetonitrile.
对比例2：Comparative example 2:
与实施例1的区别，仅在于，电解液为如下质量百分比的原料：5％二甲基嘧啶四氟硼酸盐，95％乙腈。The only difference from Example 1 is that the electrolyte is the following raw materials in mass percentage: 5% dimethyl pyrimidine tetrafluoroborate, 95% acetonitrile.
对比例3：Comparative example 3:
与实施例1的区别，仅在于，电解液为如下质量百分比的原料：40％二甲基嘧啶四氟硼酸盐，60％聚碳酸酯。The only difference from Example 1 is that the electrolyte solution is made of the following raw materials in mass percentage: 40% dimethylpyrimidine tetrafluoroborate, 60% polycarbonate.
对比例4：Comparative example 4:
与实施例1的区别，仅在于，椰壳水蒸气活化活性炭的孔径约1.5nm。The difference with Example 1 is only that the pore diameter of the activated carbon activated by coconut shell water vapor is about 1.5nm.
对比例5：Comparative example 5:
与实施例1的区别，仅在于，石油焦碱活化活性炭的孔径约2.5nm。The difference with Example 1 is only that the pore diameter of the petroleum coke-activated activated carbon is about 2.5nm.
表1：实施例1-7、对比例1-5制备的双电层电容器物理性能检测结果Table 1: Physical performance testing results of electric double layer capacitors prepared in Examples 1-7 and Comparative Examples 1-5
Figure PCTCN2022131965-appb-000001
Figure PCTCN2022131965-appb-000001
Figure PCTCN2022131965-appb-000002
Figure PCTCN2022131965-appb-000002
其中直流寿命容量保持率测试方法是额定电压/65℃浮充500h；循环寿命容量保持率测试方法是额定电压至半电压100A循环5万次后容量。Among them, the test method of DC life capacity retention rate is rated voltage/65°C float charge for 500h; the test method of cycle life capacity retention rate is the capacity after 50,000 cycles of rated voltage to half voltage 100A.
综上所述，本发明通过电解液中的阴阳离子含量的优化，对正负极多孔碳电极中多孔炭孔径的大小进行对应调整，提升了双电层电容器的单体容量和能量密度，同时本发明对电解液成分含量的优化一定程度上也提高了电容器的耐电压性能。In summary, the present invention adjusts the pore size of the porous carbon in the positive and negative porous carbon electrodes correspondingly by optimizing the content of anions and cations in the electrolyte, thereby improving the monomer capacity and energy density of the electric double layer capacitor, and at the same time The optimization of the composition content of the electrolyte in the present invention also improves the withstand voltage performance of the capacitor to a certain extent.
本处实施例对本发明要求保护的技术范围中点值未穷尽之处以及在实施例技术方案中对单个或者多个技术特征的同等替换所形成的新的技术方案，同样都在本发明要求保护的范围内，并且本发明方案所有涉及的参数间如未特别说明，则相互之间不存在不可替换的唯一性组合。The embodiments here are not exhaustive in the technical scope of the present invention, and the new technical solutions formed by the equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also claimed in the present invention. Within the scope of the present invention, and if there is no special description among all the parameters involved in the scheme of the present invention, there is no irreplaceable and unique combination among them.
本文中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种修改或补充或采用类似的方式替代，但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which the present invention pertains can make various modifications or supplements to the described specific embodiments or adopt similar methods to replace them, but they will not deviate from the spirit of the present invention or go beyond the scope defined in the appended claims.
尽管对本发明已作出了详细的说明并引证了一些具体实施例，但是对本领域熟练技术人员来说，只要不离开本发明的精神和范围可作各种变化或修正是显然的。Although the present invention has been described in detail and some specific examples have been cited, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Claims (9)

  1. 一种双电层电容器，所述电容器包括多价离子电解液、正极多孔碳电极、负极多孔碳电极、隔膜，其特征在于，正极多孔碳电极、负极多孔碳电极中多孔炭孔径均为多价离子电解液中离子粒径的3-6倍；多价离子电解液包括如下质量百分比的原料：10-35％wt的电解液盐、65-90％wt的电解液溶剂。An electric double-layer capacitor, the capacitor comprising a multivalent ion electrolyte, a positive porous carbon electrode, a negative porous carbon electrode, a diaphragm, is characterized in that the porous carbon apertures in the positive porous carbon electrode and the negative porous carbon electrode are all polyvalent The ionic electrolyte is 3-6 times the size of the ion particle; the polyvalent ion electrolyte includes the following raw materials in mass percentage: 10-35%wt electrolyte salt, 65-90%wt electrolyte solvent.
  2. 根据权利要求1所述的一种双电层电容器，其特征在于，正极多孔碳电极、负极多孔碳电极中多孔炭孔径均为多价离子电解液中离子粒径的4-5倍。An electric double layer capacitor according to claim 1, characterized in that the pore diameters of the porous carbon electrodes in the positive electrode porous carbon electrode and the negative electrode porous carbon electrode are both 4-5 times of the ion particle diameter in the polyvalent ion electrolyte.
  3. 根据权利要求1所述的一种双电层电容器，其特征在于，正极多孔碳电极与负极多孔碳电极的容量比为(1-1.5)：1。An electric double layer capacitor according to claim 1, characterized in that the capacity ratio of the positive porous carbon electrode to the negative porous carbon electrode is (1-1.5):1.
  4. 根据权利要求1所述的一种双电层电容器，其特征在于，电解液盐包括一价阴离子和二价阳离子。An electric double layer capacitor according to claim 1, wherein the electrolyte salt includes monovalent anions and divalent cations.
  5. 根据权利要求4所述的一种双电层电容器，其特征在于，一价阴离子为BF 4 -、PF 6 -、TFSI -中的一种或多种。 An electric double layer capacitor according to claim 4, characterized in that the monovalent anion is one or more of BF 4 - , PF 6 - , TFSI - .
  6. 根据权利要求4所述的一种双电层电容器，其特征在于，二价阳离子为含氮杂环的咪唑、噻唑、吡唑、嘧啶中的一种或多种。An electric double layer capacitor according to claim 4, characterized in that the divalent cation is one or more of imidazole, thiazole, pyrazole, and pyrimidine of nitrogen-containing heterocyclic rings.
  7. 根据权利要求1所述的一种双电层电容器，其特征在于，多价离子电解液中正负离子所带电荷数大于1。A kind of electric double layer capacitor according to claim 1, is characterized in that, the number of charges carried by the positive and negative ions in the polyvalent ion electrolyte is greater than 1.
  8. 根据权利要求1或2所述的一种双电层电容器，其特征在于，正极多孔碳电极中多孔炭为石油焦碱活化的活性炭。An electric double layer capacitor according to claim 1 or 2, characterized in that the porous carbon in the positive porous carbon electrode is activated carbon activated by petroleum coke.
  9. 根据权利要求1或2所述的一种双电层电容器，其特征在于，负极多孔碳电极中多孔炭为碳气凝胶或椰壳水蒸气活化的活性炭。An electric double layer capacitor according to claim 1 or 2, characterized in that the porous carbon in the negative porous carbon electrode is carbon aerogel or activated carbon activated by coconut shell water vapor.
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