CN101140828B - Technique for large-scale producing super capacitor - Google Patents

Technique for large-scale producing super capacitor Download PDF

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CN101140828B
CN101140828B CN 200710071307 CN200710071307A CN101140828B CN 101140828 B CN101140828 B CN 101140828B CN 200710071307 CN200710071307 CN 200710071307 CN 200710071307 A CN200710071307 A CN 200710071307A CN 101140828 B CN101140828 B CN 101140828B
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electrode
super
membrane
capacitors
spread
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CN 200710071307
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CN101140828A (en )
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杨晓明
范勤儒
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浙江大学宁波理工学院
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors

Abstract

The invention discloses a super-capacitors storage producing on scale, which is characterized in its manufacturing method comprising: first, spread coating membrane A, which is to spread the prepared conducting paint onto the current collectors after superficial treatment by coating machine; second, to prepare membrane B, which contains active carbon of 40% to 90%, conductive graphite of 2% to 5%and the bond of 2% to 25% in weight ratio; third, preparing the electrode material by dry process and heat pressing, which is formed by heat pressing of the membranes A and B, after which stripping it into the stripping electrode membrane by adhesive tape splitting machine; fourth, preparing the electrode by dry process, which is to clip two strips of electrode membrane in same size with isolating film by winder; fifth, putting the electrode into the aluminum super-capacitors shell, covered and keying on the positive and negative poles of the electrode by laser welding, and then infusing the electrolyte and sealed, by which the super-capacitors storage is produced.

Description

一种规模化生产的超级电容器工艺 One kind of large-scale production of super-capacitor technology

技术领域 FIELD

[0001 ] 本发明涉及超级电容器,具体地说是一种规模化生产的超级电容器工艺。 [0001] The present invention relates to a supercapacitor, in particular a large-scale production process supercapacitor.

背景技术 Background technique

[0002] 研究开发新型能源,实施节能降耗,提高环境质量是全球能源发展战略的重要内容。 [0002] Research and development of new energy sources, the implementation of energy saving and improve the quality of the environment is an important part of the global development strategy of energy. 超级电容器是近年来出现的一种能快速充/放电,超强的储能器件。 A super capacitor charged rapidly in recent years / discharging, superior energy storage device. 它兼具电容和电池的双重功能,其功能密度远高于普通电池,且比普通电池充放电速度快很多,能量密度远高于普通电解电容器,即其储能量大于普通电容器。 It combines dual-function capacitive and battery, which is much higher than ordinary batteries functional density, and much faster than the normal battery charge and discharge rate, the energy density is much higher than ordinary electrolytic capacitors, i.e., stored energy which is greater than the conventional capacitor. 与普通电容器和电池相比较,超级电容器具有体积小,容量大,充电速度快,循环寿命长,放电功率高,工作温度宽(-40°C _85°C ),可靠性好及成本低廉等优点。 Compared with the conventional battery and a capacitor, a super capacitor having small size, large capacity, charging speed, long cycle life, high discharge power, wide operating temperature (-40 ° C _85 ° C), reliability and low cost, etc. . 因此,超级电容器正在发展成为一种新型、高效、实用的储能和快速充放电设备。 Therefore, the supercapacitor is developing into a new, efficient, practical and rapid charging and discharging of the energy storage device. 在能源、通讯、数码、电子、医疗、卫生、网络、汽车等领域都有十分广泛的应用前景。 In the field of energy, telecommunications, digital, electronic, medical, health, networking, automotive and others have a very wide range of applications.

[0003] —个完整的超级电容器包含电极、电解质、集流体、隔膜四个部件。 [0003] - complete ultracapacitor comprising an electrode, an electrolyte, a current collector, a separator four members. 目前研究的超级电容器的电极材料主要有四个方面:碳电极材料,金属氧化物及其水合物电极材料,导电聚合物电极材料,以及复合电极材料。 Currently electrode material supercapacitors there are four main study: carbon electrode material, metal oxides, and hydrates electrode material, electrode material, a conductive polymer, and a composite electrode material. 碳电极材料比表面极大,原料低廉,有利于实现工业化大生产,但是比容量相对比较低。 Maximum surface area carbon electrode material, inexpensive starting material, is conducive to industrial mass production, but relatively low specific capacity. 金属氧化物及其水合物电极材料的比容量较高,但是其昂贵的成本以及对环境存在的安全隐患限制了它们的工业化规模。 Higher than the capacity of the metal oxides and hydrates electrode material, but its high cost and limited their commercial scale safety hazards occurring environment. 导电聚合物电极材料的工作电压高,从而可以提高能量存储的能力。 High voltage electrode material, a conductive polymer, which can improve the ability of the energy storage. 但是,这一类材料在有机电解质中浸泡后容易发生膨胀,造成稳定性差。 However, this type of material is easily expands was immersed in the organic electrolyte, resulting in poor stability. 复合电极材料,对电极采用不同的材料体系组成,可以提高其存储的能量密度,但是其循环的稳定性比较差。 A composite electrode material, electrode material systems of different composition, can improve the energy density stored, but relatively poor cycle stability.

[0004] 电解质需要具有很高的导电性和足够的电化学稳定性,以便超级电容器可以在尽可能高的电压下工作。 [0004] The electrolyte needs to have a sufficiently high conductivity and electrochemical stability, so that the super capacitor can operate at voltages as high as possible. 现有的电解质材料主要由固体电解质、有机物电解质和水溶液电解质。 Existing electrolyte material mainly composed of a solid electrolyte, organic electrolyte and the aqueous electrolyte. 有机物电解质的分解电压高,一般都高于2.5V,但导电性比较差;水溶液电解质主要是K0H和H2S04[H2S04],它们的分解电压受到水的分解电位的限制,只有1. 23V,但是其导电性是有机电解质的4倍以上。 High organic matter decomposition voltage of the electrolyte, generally higher than 2.5V, but relatively poor conductivity; aqueous electrolyte mainly K0H and H2S04 [H2S04], their breakdown voltage is limited by the decomposition potential of water, only 1. 23V, but more than 4 times the conductive organic electrolyte.

[0005] 隔膜的适当使用也是十分关键的。 [0005] the proper use of the diaphragm is also very critical. 有机电解质通常使用聚合物(特别是PP)或者 The organic electrolyte is usually a polymer (especially PP) or

纸作为隔膜,水溶液电解质,可以采用玻璃纤维或者陶瓷隔膜。 Paper as a separator, an aqueous solution of electrolyte, glass fiber or a ceramic membrane.

[0006] 集流体则通常是选用导电性能良好的金属和石墨等来充当。 [0006] The current collector is usually a good choice of metal and electrical conductivity to serve as graphite.

[0007] —个性能良好的超级电容器,需要以上的四个部件达到最佳优化。 [0007] - individual supercapacitor can be good, need more than four components to achieve the best optimization. 电解质和隔膜的离子电导高、隔膜具有高的电子隔离阻力,电极电子电导高、比表面积大,隔膜和电极尽量薄。 High ion conductivity of the electrolyte and a separator, the separator having a high electrical isolation resistance, high electrode electronic conductivity, large specific surface area, the separator and the electrode as thin as possible. 其中,电极材料和电解质的选择对电容量影响最大。 Wherein selecting the electrode material and the electrolyte greatest impact on capacity.

[0008] 超级电容器的电极材料是决定电容器性能的关键因素,电极材料的制备技术直接影响电极材料的性能。 [0008] The electrode material for supercapacitors is a key factor in determining the performance of the capacitor, the electrode material preparation techniques directly affect the performance of the electrode material. 因此,研究开发比容量大、电阻率小的电极材料是当务之急。 Therefore, research and development of large specific capacity, low resistance of an electrode material is a priority. 目前,大多数电极材料的粘合强度、热稳定性、耐腐蚀性、电惰性等方面均不很理想,且采用一次成型制作,其内阻大及比电容小,且不能满足大规模生产要求。 Currently, most aspects of the adhesion strength of the electrode material, thermal stability, corrosion resistance, etc. are not very satisfactory electrically inert, and production using a molding, which is smaller than the internal resistance and large capacitance, and can not meet the requirements of mass production .

[0009] 为了使超级电容器电极材料的规模化生产成为现实,电极材料的制备和工艺应有所突破和创新。 [0009] In order to make large-scale production supercapacitor electrode material to become a reality, the preparation and process of the electrode material should be a breakthrough and innovation. 超级电容器电极材料制作技术应朝热稳定性好、粘合强度高、耐腐蚀性强、 工艺简单并适于规模化生产的方向发展。 Development of super-capacitor electrode material TECHNIQUE toward thermal stability, high bonding strength, corrosion resistance, and a simple process suitable for large-scale production direction.

[0010] 涉及超级电容器电极材料制作国外部分专利如下: [0010] relates to a supercapacitor electrode material foreign part of the patent as follows:

[0011] Mitchell等人在美国专利第7227737专利公开号中介绍了双电压电容器的电极设计方法。 [0011] Mitchell et al., Describes a method of dual voltage capacitor electrode design in U.S. Patent No. 7,227,737 Patent Publication. 电极由集流体和活性电极层,即活性炭层组成。 A collector electrode and an active electrode layer, i.e., the activated carbon layer. 两个电极之间有隔离膜,将此结构浸渍在电解液中形成超级电容器。 With a separator between the two electrodes, this structure is immersed in the electrolytic solution is formed ultracapacitor. 活性电极层的厚度不同,导致不对称结构从而有不同的电容量。 Different thickness of the active layer of the electrode, thus resulting in an asymmetric structure have different capacitance. 当超级电容外加电压时,电压就不均匀地分配在次级单电容器上。 When the super capacitor voltage is applied, voltage is unevenly distributed on a single secondary capacitor. 适当选择电极层厚度可让电压在次级单电容器上均匀分布,从而提高超级电容器的极限电压。 The thickness of the electrode layer may be suitably selected so that the secondary voltage is distributed uniformly over a single capacitor, thereby enhancing the limiting voltage of the supercapacitor. [0012] zhong等人在美国专利第7147674专利公开号中介绍了浸渍处理多孔电极及其制备方法。 [0012] zhong et al describes a method of preparing porous electrodes and dipped in U.S. Patent Publication No. 7,147,674 Patent. 多性电极材料,包括活性炭、聚合物和导电碳被密封液浸渍处理,在活性电极干燥以后,密封涂料便封住了活性炭和其他多孔材料中的微孔,从而阻止了水分子和其他杂质分子移出。 Multi-electrode materials, include activated carbon, conductive carbon and polymer solution immersion treatment are sealed, after drying the active electrode, the seal will seal the activated carbon coatings other porous material and the pores, thus preventing the water molecules and molecules of other impurities removed. 但是密封涂料并不密封孔径较大的孔隙。 However, the seal coating does not seal the aperture larger pores. 此预处理的活性电极材料可用于生产超级电容的电极,被密封住的水分子不会与电解液反应,因此可以提高超级电容的极限电压。 This active electrode material may be pretreated for producing an electrode of a super capacitor, is sealed water molecules do not react with the electrolyte solution, it is possible to improve the ultimate voltage of the super capacitor.

[0013] Mitchell等人在美国专利第7102877专利公开号中介绍了电极浸渍和粘合的方法。 [0013] Mitchell et al., Describes a method of bonding of the electrode and immersed in U.S. Patent Publication No. 7,102,877 Patent. 多孔基膜的两个侧面被导电液体浸渍后由支撑膜双面支撑,然后与集流体相结合而制备电极。 Both sides of the porous substrate after the conductive film is impregnated with a liquid membrane supported by the support-sided, and then combined with the current collector to prepare an electrode. 该电极可用于能量储存设备。 The electrode can be used for energy storage devices.

[0014] Mitchell等人在美国专利第7090946专利公开号中介绍了复合电极及其制备方法。 [0014] Mitchell et al., Describes a method of preparing a composite electrode and in U.S. Patent Publication No. 7,090,946 Patent. 该复合电极由压力压制而制备,不是用粘合剂结合制备。 The composite electrode prepared by the pressing pressure, not prepared with an adhesive binding. 集流体是经过表面活化或其他表面粘合力处理的铝箔制备。 A collector or other surface preparation of the aluminum foil through the adhesive force of the surface activation treatment. 由活性炭作为活性电极材料成膜后,经过双辊塑炼,在加热下压在集流体上,从而形成电极材料。 After the active carbon as the active material forming an electrode, after two-roll mill, pressed under heating on a current collector to form an electrode material. 经过剪切成电极形状,该电极可以用于制备双层电容器等储能设备。 After cut into the shape of the electrode, the electrode can be used for the preparation of double layer capacitor energy storage device.

[0015] Bendale等人在美国专利第6955694专利公开号中介绍了一种电极制备方法。 [0015] Bendale et al describes a method for preparing an electrode in U.S. Patent No. 6,955,694 Patent Publication. 在集流体上涂布导电涂料,而且固化第一层导电涂料,然后再涂布第二层涂料并固化之,而形成电极材料。 Coating conductive paint on the current collector, and a cured first layer of conductive coating, and then applying a second coating layer and curing it to form the electrode material. 所用导电涂料是活性炭,加PVDF,聚酰胺类,溶于丙酮.丁酮J-甲基吡咯烷酮等溶剂中。 The conductive coating material is activated carbon, plus PVDF, polyamides, dissolved in acetone. Butanone J- methylpyrrolidone solvent.

[0016] Bendale等人在美国专利第6813139专利公开号中介绍了一种超级电容制备方法。 [0016] Bendale et al describes a method of preparing the super capacitor in U.S. Patent Publication No. 6,813,139 Patent. 先将铝制外壳经过加热胀大,加入电极和上下两个盖子。 First inflated heated aluminum housing, and the upper and lower electrodes covers added. 当铝壳冷却时因收縮而扣住盖子,经盖子上的小孔加入电解液至封口而制成超级电容。 When the aluminum is cooled due to shrinkage lid fastened, the apertures in the lid to seal the electrolytic solution was added to prepare a super capacitor.

[0017] Nanjundiah等人在美国专利第6804108专利公开号、第6643119专利公开号、第6631074专利公开号和第6627252专利公开号中介绍了电极制备方法。 [0017] Nanjundiah et al in U.S. Patent No. 6,804,108 Patent Publication, Publication of Patent No. 6,643,119, the Patent Publication No. 6631074 and Patent Publication No. 6627252 describes the preparation of an electrode. 在铝箔上两面涂布第一层涂料,经干燥后,再在双面涂上第二层涂料,经干燥后制备成电极材料。 On an aluminum foil applied to both surfaces of the first coating layer, after drying, coated on both sides and then a second coating layer, was prepared as an electrode material after drying. 所用导电涂料由活性炭、PVDF溶于水、丙酮、甲基纤维素、己丙基二烯丁单体等。 The conductive coating of activated carbon, PVDF was dissolved in water, acetone, methyl cellulose, propyl hexyl butyrate diene monomers.

[0018] Kurabayashi等人在美国专利第5099398专利公开号中公开了制造双电层电容器 [0018] Kurabayashi et al discloses the manufacture of an electric double layer capacitor in U.S. Patent No. 5,099,398 Patent Publication No.

的方法。 Methods. 在该专利中,电极包括连接的微小的活性炭粒子的多孔烧结体,而集电器是由诸如 In this patent, the electrode comprising a porous sintered body of fine activated carbon particles connected, such as by the collector

碳的导电材料与合成树脂或橡胶的粉末混合物制成的导电膜的形式。 Form of a conductive film of conductive material is a carbon powder with a synthetic resin or rubber mixtures prepared. 为把集电器粘合到电 For the current collector is bonded to electricity

极,由有机溶剂将集电器的表面溶解,把电极压向集电器的被溶解表面。 Electrode, the surface of the current collector is dissolved by the organic solvent, the electrode is pressed against the dissolved surface of the current collector. 当溶剂蒸发时,电 When the solvent evaporates, the electrical

极牢固地粘合到集电器,因此制造了电极和集电器之间具有低接触电阻的电极。 Very firmly bonded to the current collector, thus producing an electrode having a low contact resistance between the electrode and the current collector.

[0019] Kurabayashi等人在美国专利第5072336专利公开号中公开了制造双电层电容器 [0019] Kurabayashi et al discloses the manufacture of an electric double layer capacitor in U.S. Patent No. 5,072,336 Patent Publication No.

4的另一种方法。 4 is another method. 在该专利中,为了降低电极和集电器之间接触电阻,通过从诸如金(Au)、银(Ag)、镍(Ni)、钼(Pt)或铜(Cu)的金属蒸发而在各电极或集电器的各表面上形成导电金属膜,使电极和集电器接触。 In this patent, in order to reduce the contact resistance between the electrode and the current collector, such as by evaporation from gold (Au), silver (Ag), a nickel (Ni), molybdenum (Pt) or copper (Cu) while each of the electrodes or a conductive metal film is formed on each surface of the current collector, the electrode and the current collector in contact. 此外,他们在美国专利第5142451专利公开号和第5121301专利公开号中公开了利用各种粘合剂以类似于上述方法的方式在电极和集电器之间进行粘合的方法。 Moreover, they disclosed a method of using various binders in a manner similar to the above method for bonding between the electrode and the current collector in U.S. Patent No. 5,142,451 and Patent Publication Patent Publication No. 5,121,301.

[0020] Nishino等人在美国专利第4562511专利公开号中公开了利用形成在碳纤维或活性炭电极的表面上的金属层作为集电器的一种方法。 [0020] Nishino et al discloses the use of a metal layer formed on the surface of carbon fibers or activated carbon electrodes in U.S. Patent No. 4,562,511 Patent Publication No. As a method of a current collector. 该专利考虑了在电极的表面形成金属层的各种方法,如等离子喷涂、电弧喷镀、真空沉积、溅射、非电解质电镀和导电涂料的使用。 This patent considered various methods of forming a metal layer on the surface of the electrode, such as plasma spraying, electric arc spraying, vacuum deposition, sputtering, non-electrolytic plating, and the conductive coating.

[0021] 在美国专利第5102745、5304330和5080963专利公开号中,Tatarchuk等人公开了通过加热到金属纤维的熔点,在金属纤维形成的电极与集电器之间进行粘合的方法。 [0021] in U.S. Patent Nos. 5102745,5304330 and Patent Publication No. 5080963, Tatarchuk et al discloses a method, adhesion between the electrode and the current collector is formed by heating the metal fibers to the melting point of the metal fibers. 如下执行集电器中使用的金属纤维与电极中使用的碳纤维之间的粘合工艺。 Bonding process between the carbon fibers is performed as follows metal fiber current collector used for the electrode used. 直径大约2um的不锈钢纤维和直径为lum〜5咖的碳纤维与长度为5mm的纤维素和水通过搅动均匀地混合,然后过滤,因而形成用于电极的混合纤维合成物。 A diameter of about 2um diameter stainless steel fibers and carbon fibers lum~5 coffee and a length of 5mm cellulose and water are uniformly mixed by agitation, then filtered, thus forming a mixed fiber composite for electrodes. 该纤维合成物在模具中压成薄片。 The fiber composite pressed into a sheet in a mold. 这样制备的薄片然后经受高温和压力,以在其交叉点处粘合纤维,这样制成具有改善的内部电阻的电极。 Sheet thus prepared is then subjected to heat and pressure to bond the fibers at their crossing points, thus produced has an internal resistance of the electrode is improved. 这些专利还描述了作为粘合剂的另外的纤维,以有助于上述纤维之间的粘合。 These patents also describe the additional fiber as a binder to facilitate adhesion between the fibers. 该另外的纤维包括金属、陶瓷、碳或其任何组合。 The additional fibers include metal, ceramic, carbon, or any combination thereof.

[0022] Farahmandi等人在美国专利第5777428专利公开号和第6059847专利公开号[第5777428和6059847号]中公开了包括编织成织物的活性炭的电极。 [0022] Farahmandi et al Publication No. 6,059,847 and in U.S. Patent Publication No. 5,777,428 Patent Patent [First 5,777,428 and No. 6,059,847] discloses activated carbon electrode comprises a woven fabric. 使用铝箔作为集电器, 由利用熔化的铝浸渍过的活性炭织物来制造电极。 Using aluminum foil as a current collector, activated aluminum impregnated fabric by melting using an electrode fabricated. 在该专利中,通过在60(TC (对应于铝的熔点)以下的温度执行扩散结合技术来将铝箔结合到铝/碳合成物电极,以避免由碳与铝之间的反应而形成会显著降低电极性能的碳化铝。 In this patent, the melting point by 60 (TC (corresponding to Al) temperature of a diffusion bonding technique to bond the aluminum foil to the aluminum / carbon composite electrode is formed to avoid a reaction between carbon and aluminum is significantly reducing the aluminum carbide electrode performance.

[0023] Zuckerbrod等人在美国专利第4448856专利公开号中公开了通过利用粘合剂把活性炭与不锈钢粉末混合而制备的一种电极。 [0023] Zuckerbrod et al discloses an electrode prepared by mixing activated carbon with a stainless steel powder by using a binder in U.S. Patent No. 4,448,856 Patent Publication. 各粉末的密度限于25〜450um,将这些粉末涂覆在作为集电器的镍导线或金属片上,从而制造电极。 Density of each powder is limited 25~450um, these powder coating on the nickel wire or a metal sheet as a current collector to produce the electrode.

[0024] 上述制造活性炭或活性纤维电极的方法代表了降低活性炭电极材料与集电器之 [0024] The process for producing the activated carbon fiber electrodes or activity represent decreased activated carbon electrode material and a current collector of

间的电阻的各种工艺。 Resistance between various processes. 因为活性炭可制成纤维的形式,因而可以考虑把活性炭处理成为电 Since activated carbon can be made in the form of fibers, and thus can be considered to be electrically activated carbon treatment

极的各种方法。 Various methods poles. 但是,不可能把碳纳米管或碳纳米纤维制成纤维形式,这对制造碳纳米管电 However, it is impossible to carbon nanotubes or carbon nanofibers is made in the form of fibers, for producing carbon nanotubes that electrical

极或碳纳米纤维电极产生了限制。 Pole or carbon nanofiber electrodes had limitations. 最通用的方法是通过对碳纳米管或碳纳米纤维与粘合剂 The most common method is by carbon nanotubes or carbon nanofibers with a binder

的混合物施加压力,来制造盘形的碳纳米管电极或碳纳米纤维电极。 Mixture pressure is applied to manufacture a carbon nanotube or carbon nanofiber electrode is disc-shaped.

[0025] 涉及超级电容器电极材料制作的国内部分专利如下: [0025] relates to a supercapacitor electrode material domestic part of the patent as follows:

[0026] 付旭涛等人在中国专利公开号CN1420507A中公开一种车用超级电容器,包括第一电极、第二电极、电解液、集流体、隔膜和外壳。 [0026] Fuxu Tao et al., In Chinese Patent Publication No. CN1420507A discloses a supercapacitor vehicles, comprising a first electrode, a second electrode, electrolyte, current collector, the diaphragm and the housing. 第一电极的绝对电容量大于第二电极的绝对电容量,且第二电极中电极材料是由通过双电层原理或电容原理储存法拉第过程或二次电容原理储存能量的材料制成。 Absolute absolute capacitance of the first capacitance electrode is larger than the second electrode and the second electrode made of a material of the electrode material is stored by a capacitor or an electric double layer principles of Faraday principle during storage capacitive principle or secondary energy.

[0027] 上海奥威在中国专利公开号CN1431669 ;CN1431670 ;CN2541938 ;和CN2574196中公开一种车用启动超级电容器,其芯子由包裹隔膜的绕结成氧化锌正极片,连续化活性碳纤维布负极和集流支撑的薄膜片结构成。 Aowei [0027] In the Chinese Patent Publication No. CN1431669; CN1431670; CN2541938; and CN2574196 discloses a vehicle start supercapacitor wrapped around the core by a separator sheet to form a zinc oxide positive electrode, a negative electrode continuous activated carbon fiber cloth the film and the current collector into the support structure. 中国专利公开号CN1317809使用新材料的超级电容器极其制备方法。 Chinese Patent Publication No. CN1317809 use of new materials, their preparation methods supercapacitors. 提供了一种使用新材料形成的电极的电容器。 A capacitor is provided using a new electrode material is formed. 其包括有相互面对的两电极,这些电极由碳纳米管组成,设置在该两电极之间的电解质,和用于分离该两电极之间的电解质的分离液。 Which comprises two electrodes facing each other, these electrodes composed of carbon nanotubes, an electrolyte provided between the two electrodes, and means for separating liquid electrolyte between the two electrodes were separated. 中国专利CN1354482A :基于导电体和含氟聚合物的复合粉末极其用该粉末制造的物件。 China Patent CN1354482A: based composite powder and the conductive material extremely fluoropolymer powder produced by the object. 本发明设计一种微复合粉末,其涂布有0. 1〜0. 5um的含氟聚合物颗粒(PVDF)。 The present invention is to design a micro-composite powder, which is coated with a fluoropolymer particles 0. 1~0. 5um of (PVDF). 根据本发明的一个优选形式,微复合粉末包含成分(A、聚乙二醇),它是一种能够用于含氟聚合物或导电成分非溶剂的溶剂溶解的聚合物或齐聚物。 According to a preferred form of the invention, the micro-composite powder comprising components (A, polyethylene glycol), which is a solvent for the fluoropolymer or can be components of a non-conductive polymer or solvent soluble oligomer. 中国专利公开号CN1483212A专利发明涉及一种双层电容器,包括至少一对连接至集流器的可极化电极,插在每对电极的电极内的由离子可渗透但电子绝缘材料制成的分割层和液体电解质。 Chinese Patent Publication No. CN1483212A Patent invention relates to a double layer capacitor comprising polarizable electrodes is connected to at least one pair of current collectors, electrodes inserted in each pair of electrodes is made of an electronic but divided by an ion-permeable insulating material and a liquid electrolyte layer. 按照本发明电极具有其中纳米孔隙管分布的碳颗粒层,纳米孔隙的尺寸与电解质的离子大小匹配。 Wherein the ion having the carbon particle layer to match the size distribution of nanopores tubes, nano-size of the pores and the electrolyte electrode according to the present invention. 本发明涉及制造这种超级电容器的一种方法。 The present invention relates to a method for producing such a supercapacitor.

[0028] 李文生等人在中国专利第CN1905100A专利公开号中公开了采用聚四氟乙烯,偏氟乙烯为粘合剂,应用流延涂布方法制备活性炭电极材料。 [0028] Ocular et al disclosed in Chinese Patent Publication No. CN1905100A Patent employing polytetrafluoroethylene, polyvinylidene fluoride as a binder, preparation of activated carbon electrode material is applied cast coating method.

[0029] 李永熙等人在中国专利第CN1317809A专利公开号中公开了采用聚四氟乙烯,偏 [0029] Li Yongxi et al discloses the use of polytetrafluoroethylene in Chinese Patent Publication No. CN1317809A patent, partial

氟乙烯,酚醛树脂,聚乙烯醇,梭甲基纤维素为粘合剂的纳米碳管电极. Vinyl fluoride, phenol resin, polyvinyl alcohol, methyl cellulose shuttle nanotube electrode binder.

[0030] 谭强强等人在中国专利第CN1770344A专利公开号中公开了采用聚四氟乙烯或聚 [0030] Tan et al discloses the use of strong polytetrafluoroethylene Chinese Patent Publication No. CN1770344A patent or poly

偏四氟乙烯与N-甲基吡咯烷酮的组合物为粘合剂的电极材料. Tetrafluoroethylene and vinylidene N- methylpyrrolidone electrode material composition of the binder.

[0031] 浙江大学发明的天然矿物与纳米碳管复合超级电容器电极材料及制备方法和用Ru/C纳米复合电极材料的制备方法; [0031] The invention Zhejiang University natural mineral composite electrode material and a super capacitor and method for manufacturing nanocomposite electrode material with a Ru / C carbon nanotubes;

[0032] 中国科学院成都有机化学研究所发明的碳纳米管用于超级电容器电极材料; [0033] 北京化工大学发明的一种层状钴铝双羟基复合金属氧化物电极材料的制备方法; [0032] The carbon nanotubes, Chengdu Institute of Organic Chemistry invention for the super-capacitor electrode material; [0033] bis-hydroxy preparing composite metal oxide electrode material to a layered cobalt aluminum Beijing University of Chemical invention;

[0034] 复旦大学发明的超电容器用导电性碳包覆锂钛氧电极材料及其制备方法。 Lithium titanyl electrode material and method ultracapacitor [0034] Fudan invention is covered with a conductive carbon. 但由于偏氟乙烯粘合强度不够,且普遍使用高沸点及有毒溶剂。 However, due to insufficient adhesive strength of vinylidene fluoride, and generally high boiling point solvent and toxic. 美国多家公司尝试使用此类粘合剂,但结果均不理想。 American companies try to use such an adhesive, but the results are not satisfactory. 因此,用当前方法制备的电极材料都不能满足实际应用的需要. [0035] 现有超级电容的问题: Therefore, an electrode material prepared by the current method can not meet the needs of practical problems [0035] The conventional super capacitor:

[0036] 1、现有超级电容的极限电压不高,一般在2. 0〜2. 5伏,理论上讲,双电层超级电容的极限电压可以达到4.0伏,但是现有电极的制备方法中残留的杂质,溶剂和添加剂等限制了超级电容的极限电压。 [0036] 1, the conventional super capacitor voltage limit is not high, usually 0 to 2 2. 5 V, in theory, the electric double layer supercapacitor voltage limit of 4.0 volts can be achieved, but the conventional method of preparing an electrode residual impurities, a solvent and additives to limit the limit voltage of the super capacitor.

[0037] 2、使用寿命不长。 [0037] 2, life is not long. 现有超级电容的电极,不论是用涂布加工,还是用挤出加工,在配方中都要加入许多添加剂,如:溶剂、润滑剂、稳定剂、增塑剂、流平剂等,这些添加剂将可能与电解液发生各种反应,从而降低超级电容的极限电压和使用寿命。 Existing supercapacitor electrode, either a coating process or by an extrusion process, the formulation must be added a number of additives, such as: solvents, lubricants, stabilizers, plasticizers, leveling agents and the like, these additives various reactions occur with the electrolyte, thereby reducing the super capacitor voltage and service life limit.

[0038] 3、用涂布方法制备的电极除了添加剂和杂质影响了质量以外,其涂布厚度受到了限制,厚度不可能太厚,同时,厚度的均匀性也不理想。 [0038] 3, the electrode prepared by applying a method other additives and impurities affect the quality of the outside, which coating thickness is limited, the thickness can not be too thick, while the thickness uniformity is not satisfactory. 如果分两次或多次涂布,同样也存在不均匀性、杂质等问题。 If the coating twice or more times, the same problem also exists unevenness and impurities.

发明内容 SUMMARY

[0039] 本发明的目的在于克服现有技术超级电容电极粘合强度低,能量密度不高和生产成本高等缺点,提供一种快速充放电、一种规模化生产的超级电容器工艺,它将提高活性炭和导电碳在电极中分布均匀性和一致性;提高电极薄膜的强度;降低电极的内阻;增加表面积;使用无添加剂的干法制备方法。 [0039] The object of the present invention to overcome the prior art super-capacitor lower electrode adhesion strength is not high energy density and high cost of production, to provide a rapid charging and discharging a supercapacitor production scale process, it will improve activated carbon and conductive carbon uniformly distributed in the electrode and consistency; increase the film strength of the electrode; reduce the internal resistance of the electrode; increasing the surface area; method manufactured using dry method without additives. CN 101140828 B CN 101140828 B

[0040] 本发明解决上述技术问题所采用的技术方案为: [0041] —种规模化生产的超级电容器工艺,该制备工艺包括: [0042] (1)涂布导电基膜,即A膜: [0040] aspect of the present invention to solve the above technical problem is: [0041] - scale production species supercapacitor process, the preparation process comprises: [0042] (1) applying a conductive base film, i.e., film A:

[0043] 将制备好的导电涂料用涂布机涂布在经过表面处理的集流体上,所述的涂布机是凹板网纹涂布头,涂布机烘箱温度为40〜ll(TC,按照梯度分布在各段烘箱,涂布机的涂布速度为5〜80m/min,涂布量是2〜10g/m2,涂布厚度是4〜12um, A膜为条状涂布,涂布的线条宽度误差范围是0〜1. 5mm, A膜为双面涂布,双面涂布的线条宽度误差范围是0〜 1.5mm,A膜的电阻值小于30mQ ; [0044] (2)制备复合导电基膜,即B膜: [0043] The prepared electroconductive paint coater on the current collector surface treated, the gravure coating machine is textured coating head coater oven temperature 40~ll (TC according to a coating speed gradient distribution in each segment oven, the coater was 5~80m / min, the coating amount is 2~10g / m2, the coating thickness is 4~12um, a stripe coating film, coating cloth line width error range is 0~1 5mm, a double-coated film coated on both sides of the line width error range 0~ 1.5mm, the resistance value of the film is less than a 30mQ;. [0044] (2) preparation of composite conductive base film, i.e., film B:

[0045] 所述的B膜含活性炭重量比为40〜99%,含导电石墨重量比为2〜50%,含粘合剂重量比为2〜25% ; B film [0045] The weight ratio of the activated carbon-containing 40~99% by weight of conductive graphite-containing 2~50%, by weight of the binder-containing 2~25%;

[0046] 活性炭是XC-72和GH-3892中的一种或两种按任意比例混合,来自Cabont公司;导电石墨是K56和AB-065M中的一种或两种按任意比例混合,来自Timcal Gr即hite andCarbon公司;粘合剂是热塑性塑料,可挤出加工成膜,粘合剂是乙烯_四氟乙烯共聚物; [0046] Activated carbon is XC-72 and GH-3892 in one or both in any mixing ratio, from Cabont company; and conductive graphite is K56 AB-065M in one or both of mixing in any ratio, from Timcal Gr i.e. hite andCarbon Corporation; binder is a thermoplastic, extrudable film-forming process, the binder is an ethylene tetrafluoroethylene copolymer _;

[0047] B膜是活性炭、导电石墨和粘合剂三种粉末料经过干粉混合均匀而成的混合粉末, 干粉混合是在高速混合机中完成的; [0047] B is a film of activated carbon, conductive graphite, and a binder of the three powders were fed through dry mixed powder obtained by mixing, dry mixing is done in a high speed mixer;

[0048] B膜是由三辊塑炼机制备的,三辊塑炼机的塑炼温度的温度范围是300〜50(TC, 塑炼时间是10〜120分钟,所制备的B膜的长度是1〜2000米,厚度是50〜500um ; [0049] (3)干法热压制备电极材料: [0048] B film by a three-roll mill is prepared mechanisms, temperature mastication temperature range three-roll mill is 300~50 (TC, mastication time is 10~120 minutes, the length of the film B prepared m is 1~2000, thickness 50~500um; [0049] (3) preparation of dry hot electrode material:

[0050] 由A膜和B膜经加热压制而成,然后通过胶带分切机分条制成分条电极膜; [OO51] (4)干法制备电极: [0050] A film and the B film formed by pressing a heated, Articles electrode film made of component tape is then divided by the slitter; [OO51] (4) Dry Method electrode prepared:

[0052] 在巻绕机上将两条相同尺寸的分条电极膜夹上隔离膜制备而成电极,巻绕机的芯子直径为5〜200mm,巻绕的芯子高度为5〜200mm ; [0052] In the spacer clip Volume electrode film slitting machine on about the same size as the two films prepared from the electrode, Volume rewinder mandrel having a diameter of 5~200mm, Volume wound core height 5~200mm;

[0053] (5)将电极放入铝制超级电容壳内,盖上盖子,经过激光焊接接通电极的正负极, [0053] (5) The super-capacitor electrode placed in an aluminum housing, cover, after turning on the laser welding of the positive and negative electrodes,

注进电解液,再封口便制成超级电容器。 Injected into the electrolyte, and then seal it made a super capacitor.

[0054] 所述的涂布机的最佳涂布速度为25〜55m/min。 Optimal coating rate [0054] The coating machine was 25~55m / min.

[0055] 所述的A膜的最佳方案是:涂布量是2. 8〜5. 2g/tf,涂布厚度是6〜10um, A膜是条状涂布,涂布的线条宽度误差范围是0〜0. 5mm, A膜是双面涂布,双面涂布的线条宽度误差范围是O〜0. 5mm。 [0055] A film of the best solution is that: the coating amount is 2. 8~5 2g / tf, the thickness of the coating is 6~10um, A stripe coating film is a coating line width error. in the range of 0~0. 5mm, a double-sided coated film is coated on both sides of the line width error range O~0. 5mm.

[0056] 所述的B膜的最佳方案是:含活性炭重量比为60〜80% ,导电石墨重量比为10〜 20%,粘合剂重量比为10〜20%。 Best film B [0056] a is: containing ratio of 60~80% by weight of activated carbon, conductive graphite ratio is 10~ 20% by weight, of 10-20% by weight binder.

[0057] 所述的B膜是由三辊塑炼机制备的,其的最佳工艺为:三辊塑炼机的塑炼温度的温度范围是320〜38(TC,塑炼时间是30〜40分钟,所制备的B膜的长度是1000〜2000 米,厚度是100〜250um。 B film [0057] the three-roll mill is prepared mechanism, which is optimum: mastication temperature three-roll mill temperature range is 320~38 (TC, mastication time is 30~ 40 minutes, the length of the B film is prepared 1000~2000 m, thickness 100~250um.

[0058] 本发明超级电容器的制备工艺包括:导电涂布基膜-A膜制备方法、复合导电基膜-B膜干法制备技术、干法热压制备电极材料、电极的干法制备方法。 Preparation [0058] The present invention supercapacitors comprising: preparing a conductive film coating the base film -A, -B base film conductive composite membrane prepared dry process technique to prepare an electrode material dry pressing, an electrode prepared by a dry method. [0059] 1、导电涂布基膜-A膜制备方法:用喷涂涂布机,凹板网纹涂布机,钢丝刮刀涂布机或其他相似涂布机均可。 [0059] 1, preparation of the conductive film coating the base film -A: with a spray coater, gravure coater textured, knife coater, wire coater or other similar available. 用汽流式、主动式或被动式导辊,用电加热、油加热或者汽加热 Steam flow, active or passive guide rollers, electric heating, oil heating or steam heating

7均可,烘箱温度从40〜12(TC不等,梯度分布于不同烘箱段,涂布速度以10米/秒到80米/秒不等,根据烘箱长度、温度和涂层厚度决定。将导电涂料加入进料槽,铝箔放在一放导辊上,开动涂布机,待铝箔移动平稳无打皱时,开始涂布。涂布的温度和厚度根据电极尺寸设计而决定。但厚度公差在士2um,宽度公差在±0. 5mm,双面对齐的公差在±0. 5mm。 [0060] 2、复合导电基膜-B膜干法制备技术: 7 may, from the oven temperature 40~12 (TC range, oven gradient distributed across different segments, coating speed range, determined at 10 m / s to 80 m / s in accordance with the length of the oven, and the temperature of the coating thickness. The added conductive paint feed chute, placed on aluminum foil on a guide roller coater start to be moved smoothly without the aluminum foil wrinkled, coating start. temperature and thickness of the coating is determined according to the size of the electrode design, but the thickness tolerance in persons 2um, width tolerance 5mm, double-sided alignment tolerances 0 ± 0 ± 5mm [0060] 2, -B composite conductive base film dry film Preparation technology...:

[0061 ] a、导电基膜-B膜的最佳配方设计;多孔碳50 %〜99 % 、导电剂0 %〜25 % 、含氟聚合物粘结剂1 %〜25 % .更进一步的最佳配方是:多孔碳80%〜95 % 、导电剂0%〜 15%、含氟聚合物粘结剂3%〜15% . [0061] The optimum formulation a, a conductive film, the base film -B; 50% ~99% porous carbon, conductive agent, 0% ~ 25%, a fluoropolymer binder further 1% ~ 25% most. best formula is: 80% ~ 95% porous carbon, conductive agent, from 0% to 15%, a fluoropolymer binder 3% ~ 15%.

[0062] b、导电基膜-B膜的制备方法:导电基膜的制备经过三辊塑炼机加热塑炼的方法制备成型。 [0062] b, -B preparing a conductive base film layer: preparing a conductive base film after mastication method of preparing three-roll mill heated molding. 先将粉末物料经过充分均匀混合后,三辊机擦洗干净后,将前后辊稍放松一些, 向后辊与中辊之间加入物料,开动电机,3个辊以不同速度开始转动。 First powder material after sufficiently uniformly mixed and cleaned three-roll mill, the front and rear rollers relax slightly, the material was added between the rear rollers and the roller, the motor start, three rollers start rotating at different speeds. 同时调整前辊与中辊的间距,务使三辊的三条中心线平行,防止把辊子对斜。 While adjusting the pitch of the front roller and the roller, parallel to the centerline three Wushi three rollers to prevent the swash roller. 后辊与中辊之间装有一对挡板,防止料浆外溢,当两辊向内转动时,料浆被扯到加料缝,这道缝空间逐渐狭窄,大部分料浆不能通过,而因两辊转动使料浆在加料沟里循环。 Between the roller and the roller is provided with a pair of baffles, to prevent slurry spills, when the two rolls is rotated inwardly, the slurry is fed side-tracked joint, which space gradually narrowed passage slit, the slurry can not pass through most, but due to rotation of the two rollers feed the slurry circulating in the ditch. 大颗粒被斥回料浆顶部,小颗粒通过辊内缝隙并分成两部分,一部分附在后辊上,一部分附在中辊上。 Large particles are repellent back to the top of the slurry, the small particles by the roller slit and divided into two portions, a roll, a portion of the roller attached to the attached portion. 后辊上的那部分回到加料沟,中辊上那部分传递到中辊和前辊之间。 After the portion on the back feed roller groove, passed between the roller and the front portion of the roll that the roll. 如此多次循环便获得均匀混合后的物料,再经冷却成片而制成导电基膜,膜厚度是100-250um,长度最小1米。 Multiple cycles would thus obtained material after uniformly mixed, and then cooled into a sheet and made of a conductive base film, the film thickness is 100-250um, the minimum length of 1 meter.

[0063] 3、电极材料干法制备方法:将导电基膜-B膜与涂有导电涂料的集流体-A膜,在加热加压下压制成型,制成电极基膜。 [0063] 3, the electrode material prepared by a dry process method: the conductive film and the base film -B -A collector coated film electrically conductive coating, press-molded under heat and pressure to prepare an electrode base film.

[0064] 4、超级电容电极制备方法:将制成的电极膜安装在巻绕机上,同时安装绝缘隔离膜,开动巻绕机制备直径为25-50mm和高度为30-80mm的芯子,在100〜150°C [100-150C] 真空干燥8-12小时,制得超级电容的电极。 [0064] 4. Preparation super capacitor electrode: electrode film formed on the mounting Volume rewinding machine, install the insulating separator, Volume actuating mechanism with a diameter of about 25-50mm and 30-80mm height of the core, the 100~150 ° C [100-150C] was dried under vacuum for 8-12 hours to prepare a super capacitor electrode.

[0065] 5、将电极放入铝制超级电容壳内,盖上盖子,经过激光焊接接通电极的正负极,注进电解液,再封口便制成超级电容器。 [0065] 5, the super capacitor electrodes placed in an aluminum housing, cover, after turning on the laser welding of the positive and negative electrodes, an electrolyte injected into, then made reclosable supercapacitor.

[0066] 由于本发明采取了上述的技术措施,它与现有技术相比具有如下优点: [0066] Since the present invention takes the technical measures described above, it is compared with the prior art has the following advantages:

[0067] 1、具有良好的耐温性、耐腐蚀性及电极制作所要求的机械物理特性; [0067] 1, has good heat resistance, corrosion resistance and mechanical and physical properties required for electrode fabrication;

[0068] 2、由于导电基模A模、B模制作中未添加润滑剂、稳定剂、增塑剂、流平剂等,因此, [0068] 2, since the conductive fundamental mode A mode, B mode is not produced lubricant, a stabilizer, a plasticizer, a leveling agent, therefore,

增强了电化学性能稳定性,从而延长了超级电容器的使用寿命; Enhanced electrochemical performance stability, thus extending the life of the supercapacitors;

[0069] 3、由于采用电极材料干法制备物理方法制备电极材料,生产工艺简单、适应于规模化制备超级电容器、并对环境友好。 [0069] 3, since the material is prepared by preparing an electrode using an electrode material physically dry, simple production process, to adapt to large-scale preparation of supercapacitors, and is friendly to the environment.

附图说明 BRIEF DESCRIPTION

[0070] 图1是本发明实施例的电极基膜结构示意图; [0070] FIG. 1 is a schematic view of the electrode structure of the embodiment of the base film of the present invention;

[0071] 图2是本发明实施例的超级电容器单体的正面结构示意图; [0071] FIG. 2 is a schematic front view showing the structure of the monomer supercapacitor embodiment of the present invention;

[0072] 图3是本发明实施例的超级电容器单体的纵向截面结构示意图。 [0072] FIG. 3 is a schematic longitudinal section of a supercapacitor monomer embodiment of the present invention.

[0073] 图中:1为正极柱,2为负极柱,3为正极片,4为负极片,5为多孔绝缘隔膜,6为电 [0073] FIG: 1 is a positive column, a column 2 as a negative electrode, a positive electrode sheet 3, a negative electrode sheet 4, a porous insulating separator 5, 6 is electrically

解液,7为集电体,8为封装外壳,9为导电基膜,10为集电极铝箔。 Liquid solution, the current collector 7, 8 of the package housing, a conductive base film 9, the collector 10 is an aluminum foil. 具体实施方式 detailed description

[0074] 以下结合附图和实施例对本发明作进一步详细描述。 [0074] Hereinafter, the present invention is described in further detail in conjunction with the accompanying drawings and embodiments. [0075] 实施例1 : [0075] Example 1:

[0076] 参照附图,将导电涂料加入进料槽,集电极铝箔IO经过表面处理后,厚度为20士2um,宽度为500±2mm,长度为2000〜3000m。 [0076] Referring to the drawings, a conductive coating material is added into the tank, the collector foil IO after surface treatment, a thickness of 20 persons 2um, a width of 500 ± 2mm, a length of 2000~3000m. 放在涂布机一放导辊上,开动涂布机,涂布机用凹板网纹涂布,烘箱温度为40〜ll(TC,涂布速度为35米/分钟,涂布量为4. 0± 1. 2g/m2,涂布厚度为8士2um,涂布密度为0. 5±0. 25g/cm3,星条状双面涂布,线条宽度为85±0. 5mm,双面对齐精度为±0. 5mm,外观需无杂质,无白点,无皱纹,无巻边,无气泡等缺陷,制备导电基膜9为A膜。 [0077] 导电涂料由以下方法制得: [0078] 粘合剂配方: A coater placed on the discharge guide roller start coater, gravure coater with a textured coating, oven temperature 40~ll (TC, coating speed of 35 m / min, the coating amount of 4 . 0 ± 1. 2g / m2, the coating thickness of 8 persons 2um, coating density of 0. 5 ± 0. 25g / cm3, star double coated strip, the line width was 85 ± 0. 5mm, two-sided alignment accuracy of ± 0 5mm, appearance is required and no impurities, no white spots, no wrinkles, no Volume edges, no bubbles and other defects, preparing a conductive base film 9 is a film A [0077] conductive coating obtained by the following methods: [ 0078] adhesive formulations:

[0079] 水溶性乙烯_丙烯酸酯共聚乳液UCAR Latex 300 :15重量份,Surfynol OP-340 : 0. 5重量份,DF-110D :0. 1重量份,CT-136 :1重量份。 [0079] _ water-soluble vinyl acrylate copolymer emulsion 300 UCAR Latex: 15 parts by weight, Surfynol OP-340: 0. 5 parts by weight, DF-110D:. 0 1 parts by weight, CT-136: 1 parts by weight. [0080] 将上述原料溶于83. 4重量份的水中制得粘合剂。 [0080] The above material was dissolved in 83.4 parts by weight of water to prepare a binder.

[0081] 粘合剂在导电涂料中重量比为20X;高表面积活性炭使用XC-72,在导电涂料中的重量比为60% ;石墨电极材料选用Timrex的K56导电石墨,在导电涂料中重量比为20%。 [0081] In the conductive adhesive in a weight ratio of coating material 2OX; high surface area active carbon XC-72, the weight ratio of the conductive coating 60%; K56 graphite electrode conductive graphite Timrex material selection, the weight ratio of the conductive coating 20%. [0082] 将粘合剂、活性炭、石墨和水加入料槽中,开动高速剪切搅拌机,转速逐渐加速到1000n/min,连续搅拌2〜3小时,在搅拌中,液体温度升高到30〜40°C ,并产生一些气泡, 然后停止搅拌,用过滤袋过滤后,静止待用。 [0082] The binder, activated carbon, graphite and water were added to the trough, a high shear mixer start, speed gradually accelerated to 1000n / min, 2 to 3 hours of continuous stirring, the stirring, the liquid temperature was raised to 30~ 40 ° C, and causing some bubbling, and stirring was stopped, the bag filter used, still stand. 导电涂料电阻值《30mQ,pH 8-9,固含量25〜 35%,粘合范围:50〜300cps。 Conductive coating resistance value "30mQ, pH 8-9, 25~ 35% solids content, adhesion spectrum: 50~300cps.

[0083] 导电干复合基膜B膜由活性炭,XC-72/GH-3892重量比为70%,石墨为K56/ AB-065M重量比为15%,粘合剂为乙烯-四氟乙烯共聚物重量比为15%,来自于杜邦。 [0083] Stem composite conductive base film B film of activated carbon, XC-72 / GH-3892 weight ratio of 70% graphite K56 / AB-065M is 15% by weight, the binder is an ethylene - tetrafluoroethylene copolymer 15% by weight, from DuPont. 将三种粉末在高速混合机中干混均匀,约30分钟,然后将三辊塑炼机加热到30(TC,将物料慢慢加入三辊塑炼机上进行塑炼大约30分钟,然后制备成一米以上的复合导电B膜。厚度为100〜250um。然后将导电基膜A与B经压碾机在加热到温度30(TC时压制成电极基膜。 [0084] 将电极基膜按超级电容尺寸要求分切成条并巻绕成一巻供制备超级电容使用。 [0085] 将两巻电极材料,80um多孔绝缘隔膜5分别放在巻绕机上,巻绕成直径为50mm高80mm的芯子,并在15(TC下,真空干燥8小时后,将其放入铝制壳中,并将加热后的上、下两个盖子盖上,待盖子冷却后,即牢牢的卡在铝壳上,然后再用激光焊接方法将电极的正极片3和负极片4分别焊在正极柱1和负极柱2上。然后由盖子上的小孔,在干燥室内,加入电解液6,并封口而制出3000法拉的超级电容。 [0086] 实施例2 : The three powders in a high speed mixer uniformly dry blended for about 30 minutes, and then the three-roll mill heated to 30 (TC, the material was added slowly masticated for about 30 minutes on a three-roll mill, and then prepared into a B m above a conductive composite film. the thickness of 100~250um. then the conductive base film a and B by pressing mill heated to a temperature of 30 (electrode base film when pressed into TC. [0084] the base film according to the super capacitor electrode and cut into the required size fraction Volume Volume wound into a super capacitor used for preparation. [0085] the two Volume electrode material, a porous insulating separator 5 80um respectively on Volume rewinding machine, Volume wound core having a diameter of 50mm to 80mm in height, and (the TC 15, vacuum dried for 8 hours, it was placed in an aluminum housing, and the heated, the two lid on the lid after cooling, i.e. firmly stuck in the aluminum and then laser welding the positive electrode sheet and negative electrode sheet 3, 4 are welded to the positive electrode pole and negative electrode pole 1 2. then a small hole on the lid, the drying chamber, the electrolytic solution 6 was added, and the system sealed . 3000 farad super capacitor out of [0086] Example 2:

[0087] 参照附图,将导电涂料加入进料槽,集电极铝箔IO经过表面处理后,厚度为20士2um,宽度为500士2mm,长度为2000〜3000m。 [0087] Referring to the drawings, a conductive coating material is added into the tank, the collector foil IO after surface treatment, a thickness of 20 persons 2um, a width of 500 persons 2mm, a length of 2000~3000m. 放在涂布机一放导辊上,开动涂布机,涂布机用凹板网纹涂布,烘箱温度为40〜ll(TC,涂布速度为35米/分钟,涂布量为4. 0± 1. 2g/m2,涂布厚度为8士2um,涂布密度为0. 5±0. 25g/cm3,星条状双面涂布,线条宽度为85±0. 5mm,双面对齐精度为±0. 5mm,外观需无杂质,无白点,无皱纹,无巻边,无气泡等缺陷,制备导电基膜9为A膜。 [0088] 导电涂料由以下方法制得: A coater placed on the discharge guide roller start coater, gravure coater with a textured coating, oven temperature 40~ll (TC, coating speed of 35 m / min, the coating amount of 4 . 0 ± 1. 2g / m2, the coating thickness of 8 persons 2um, coating density of 0. 5 ± 0. 25g / cm3, star double coated strip, the line width was 85 ± 0. 5mm, two-sided alignment accuracy of ± 0 5mm, appearance is required and no impurities, no white spots, no wrinkles, no Volume edges, no bubbles and other defects, the base film 9 to prepare a conductive film A [0088] conductive coating obtained by the following methods.:

9[0089] 粘合剂配方: 9 [0089] The adhesive formulation:

[0090] 水溶性乙烯_丙烯酸酯共聚乳液UCAR Latex 357 :10重量份,Surfynol 0P-340 : 0. 5重量份,DF-110D :0. 1重量份,CT-136 :1重量份。 [0090] _ water-soluble vinyl acrylate copolymer emulsion 357 UCAR Latex: 10 parts by weight, 0P-340 Surfynol: 0. 5 parts by weight, DF-110D:. 0 1 parts by weight, CT-136: 1 parts by weight. [0091] 将上述原料溶于88. 4重量份的水中制得粘合剂。 [0091] The above material was dissolved in 88.4 parts by weight of water to prepare a binder.

[0092] 涂料粘合剂在导电涂料中重量比为15X;高表面积活性炭使用XC-72,在导电涂料中重量比为70X;石墨电极材料选用Timrex的K56导电石墨,在导电涂料中重量比为15X。 [0092] In the conductive paint coating binder weight ratio of 15X; high surface area active carbon XC-72, in a weight ratio of electrically conductive paint 70X; K56 conductive graphite Timrex graphite electrode material selection and the conductive coating in a weight ratio of 15X. [0093] 将粘合剂,活性炭,石墨和水加入料槽中,开动高速剪切搅拌机,转速逐渐加速到1000n/min,连续搅拌2〜3小时,在搅拌中,液体温度升高到30〜40°C ,并产生一些气泡, 然后停止搅拌,用过滤袋过滤后,静止待用。 [0093] The binder, activated carbon, graphite and water were added to the trough, a high shear mixer start, speed gradually accelerated to 1000n / min, 2 to 3 hours of continuous stirring, the stirring, the liquid temperature was raised to 30~ 40 ° C, and causing some bubbling, and stirring was stopped, the bag filter used, still stand. 导电涂料电阻值《30m Q , pH值为8-9,固含量25〜35%,粘合性:50〜300cps。 Conductive coating resistance value "30m Q, pH value of 8-9, a solids content of 25~35%, adhesion: 50~300cps.

[0094] 导电干复合基膜B膜由活性炭,XC-72/GH-3892重量比为70%,石墨为K56/ AB-065M重量比为15%,粘合剂为乙烯-四氟乙烯共聚物重量比为15%,来自于杜邦。 [0094] The dry composite conductive base film B film of activated carbon, XC-72 / GH-3892 weight ratio of 70% graphite K56 / AB-065M is 15% by weight, the binder is an ethylene - tetrafluoroethylene copolymer 15% by weight, from DuPont. 将三种粉末在高速混合机中干混均匀,约30分钟,然后将三辊塑炼机加热到30(TC,将物料慢慢加入三辊塑炼机上进行塑炼大约30分钟,然后制备成一米以上的复合导电B膜。厚度为100〜250um。然后将导电基膜A与B经压碾机在加热到温度30(TC时压制成电极基膜。 [0095] 将电极基膜按超级电容尺寸要求分切成条并巻绕成一巻供制备超级电容使用。 [0096] 将两巻电极材料,80um多孔绝缘隔膜分别放在巻绕机上,巻绕成直径为50mm高80mm的芯子,并在15(TC下,真空干燥8小时后,将其放入铝制壳中,并将加热后的上、下两个盖子盖上,待盖子冷却后,即牢牢的卡在铝壳上,然后再用激光焊接方法将电极的正极片3和负极片4分别焊在正极柱1和负极柱2上。然后由盖子上的小孔,在干燥室内,加入电解液6,并封口而制出3000法拉的超级电容。 [0097] 实施例3 : The three powders in a high speed mixer uniformly dry blended for about 30 minutes, and then the three-roll mill heated to 30 (TC, the material was added slowly masticated for about 30 minutes on a three-roll mill, and then prepared into a B m above a conductive composite film. the thickness of 100~250um. then the conductive base film a and B by pressing mill heated to a temperature of 30 (electrode base film when pressed into TC. [0095] the base film according to the super capacitor electrode and cut into the required size fraction Volume Volume wound into a super capacitor used for preparation. [0096] the two Volume electrode material, a porous insulating separator 80um respectively on Volume rewinding machine, Volume wound core of 50mm in diameter and 80mm in height and in (the TC 15, vacuum dried for 8 hours, it was placed in an aluminum housing, and the heated, the two lid on the lid after cooling, i.e. firmly on the aluminum card, then use the laser welding method of the positive electrode and the negative electrode sheets 3 sheets 4 are respectively welded to the positive electrode pole and negative electrode pole 1 2. then a small hole on the lid, the drying chamber, the electrolytic solution 6 was added, and the sealed prepared . 3000 farad super capacitor [0097] Example 3:

[0098] 参照附图,将导电涂料加入进料槽,集电极铝箔IO经过表面处理后,厚度为20士2um,宽度为500士2mm,长度为2000〜3000m。 [0098] Referring to the drawings, a conductive coating material is added into the tank, the collector foil IO after surface treatment, a thickness of 20 persons 2um, a width of 500 persons 2mm, a length of 2000~3000m. 放在涂布机一放导辊上,开动涂布机,涂布机用凹板网纹涂布,烘箱温度为40〜ll(TC,涂布速度为35米/分钟,涂布量为4. 0± 1. 2g/m2,涂布厚度为8士2um,涂布密度为0. 5±0. 25g/cm3,星条状双面涂布,线条宽度为85±0. 5mm,双面对齐精度为±0. 5mm,外观需无杂质,无白点,无皱纹,无巻边,无气泡等缺陷,制备导电基膜9为A膜。 [0099] 导电涂料由以下方法制得: [0100] 粘合剂配方: A coater placed on the discharge guide roller start coater, gravure coater with a textured coating, oven temperature 40~ll (TC, coating speed of 35 m / min, the coating amount of 4 . 0 ± 1. 2g / m2, the coating thickness of 8 persons 2um, coating density of 0. 5 ± 0. 25g / cm3, star double coated strip, the line width was 85 ± 0. 5mm, two-sided alignment accuracy of ± 0 5mm, appearance is required and no impurities, no white spots, no wrinkles, no Volume edges, no bubbles and other defects, preparing a conductive base film 9 is a film A [0099] conductive coating obtained by the following methods: [ 0100] adhesive formulations:

[0101] 水溶性乙烯-丙烯酸酯共聚乳液UCAR Latex 300 :5重量份,Surfynol 0P-340 : 0. 5重量份,DF-110D :0. 1重量份,CT-136 :1重量份。 [0101] water-soluble ethylene - acrylate copolymer emulsion 300 UCAR Latex: 5 parts by weight, 0P-340 Surfynol: 0. 5 parts by weight, DF-110D: 0 1 parts by weight, CT-136: 1 parts by weight. [0102] 将上述原料溶于93. 4重量份的水中制得粘合剂。 [0102] The above material was dissolved in 93.4 parts by weight of water to prepare a binder.

[0103] 粘合剂在导电涂料中重量比为10X;高表面积活性炭使用XC-72,在导电涂料中重量比为80% ;石墨电极材料选用Timrex的K56导电石墨,在导电涂料中重量比为10%。 [0103] In the conductive adhesive in a weight ratio of coating material 10X; high surface area active carbon XC-72, in a weight ratio of the conductive coating 80%; K56 conductive graphite Timrex graphite electrode material selection and the conductive coating in a weight ratio of 10%. [0104] 将粘合剂,活性炭,石墨和水加入料槽中,开动高速剪切搅拌机,转速逐渐加速到1000n/min,连续搅拌2〜3小时,在搅拌中,液体温度升高到30〜40°C ,并产生一些气泡, 然后停止搅拌,用过滤袋过滤后,静止待用。 [0104] The binder, activated carbon, graphite and water were added to the trough, a high shear mixer start, speed gradually accelerated to 1000n / min, 2 to 3 hours of continuous stirring, the stirring, the liquid temperature was raised to 30~ 40 ° C, and causing some bubbling, and stirring was stopped, the bag filter used, still stand. 导电涂料电阻值《30m Q , pH值为8-9,固含量25〜35%,粘合性:50〜300cps。 Conductive coating resistance value "30m Q, pH value of 8-9, a solids content of 25~35%, adhesion: 50~300cps. [0105] 导电干复合基膜B膜由活性炭,XC-72/GM-3892重量比为70%,石墨为K56/ AB-065M重量比为15%,粘合剂为乙烯-四氟乙烯共聚物重量比为15%,来自于杜邦。 [0105] Stem composite conductive base film B film of activated carbon, XC-72 / GM-3892 was 70% by weight, graphite K56 / AB-065M is 15% by weight, the binder is an ethylene - tetrafluoroethylene copolymer 15% by weight, from DuPont. 将三种粉末在高速混合机中干混均匀,约30分钟,然后将三辊塑炼机加热到30(TC,将物料慢慢加入三辊塑炼机上进行塑炼大约30分钟,然后制备成一米以上的复合导电B膜。厚度为100〜250um。然后将导电基膜A与B经压碾机在加热到温度30(TC时压制成电极基膜。 [0106] 将电极基膜按超级电容尺寸要求分切成条并巻绕成一巻供制备超级电容使用。 [0107] 将两巻电极材料,80um多孔绝缘隔膜分别放在巻绕机上,巻绕成直径为50mm高80mm的芯子,并在15(TC下,真空干燥8小时后,将其放入铝制壳中,并将加热后的上、下两个盖子盖上,待盖子冷却后,即牢牢的卡在铝壳上,然后再用激光焊接方法将电极的正极片3和负极片4分别焊在正极柱1和负极柱2上。然后由盖子上的小孔,在干燥室内,加入电解液6,并封口而制出3000法拉的超级电容。 The three powders in a high speed mixer uniformly dry blended for about 30 minutes, and then the three-roll mill heated to 30 (TC, the material was added slowly masticated for about 30 minutes on a three-roll mill, and then prepared into a B m above a conductive composite film. the thickness of 100~250um. then the conductive base film a and B by pressing mill heated to a temperature of 30 (electrode base film when pressed into TC. [0106] the base film according to the super capacitor electrode and cut into the required size fraction Volume Volume wound into a super capacitor used for preparation. [0107] the two Volume electrode material, a porous insulating separator 80um respectively on Volume rewinding machine, Volume wound core of 50mm in diameter and 80mm in height and in (the TC 15, vacuum dried for 8 hours, it was placed in an aluminum housing, and the heated, the two lid on the lid after cooling, i.e. firmly on the aluminum card, then use the laser welding method of the positive electrode and the negative electrode sheets 3 sheets 4 are respectively welded to the positive electrode pole and negative electrode pole 1 2. then a small hole on the lid, the drying chamber, the electrolytic solution 6 was added, and the sealed prepared Farah super capacitor of 3000.

Claims (5)

  1. 一种规模化生产的超级电容器工艺,其特征是:该制备工艺包括:(1)涂布导电基膜,即A膜:将制备好的导电涂料用涂布机涂布在经过表面处理的集流体上,所述的涂布机是凹板网纹涂布头,涂布机烘箱温度为40~110℃,按照梯度分布在各段烘箱,涂布机的涂布速度为5~80m/min,涂布量是2~10g/m2,涂布厚度是4~12um,A膜为条状涂布,该涂布的线条宽度误差范围是0~1.5mm,A膜为双面涂布,双面涂布的线条宽度误差范围是0~1.5mm,A膜的电阻值小于30mΩ;(2)制备复合导电基膜,即B膜:所述的B膜含活性炭重量比为40~90%,含导电石墨重量比为2~50%,含粘合剂重量比为2~25%;活性炭是XC-72和GH-3892中的一种或两种按任意比例混合,来自Cabont公司;导电石墨是K56和AB-065M中的一种或两种按任意比例混合,来自Timcal?Graphite?andCarbon公司;粘合剂是热塑性塑料,可 One kind of process-scale production of super capacitor, wherein: the preparation process comprises: (1) applying a conductive base film, i.e. A film: The conductive coating prepared by the coater surface-treated collector fluid, the gravure coating machine is textured coating head coater oven temperature is 40 ~ 110 ℃, according to the gradient profile in an oven at a coating speed of each segment, the coater is 5 ~ 80m / min , the coating amount is 2 ~ 10g / m2, the coating thickness is 4 ~ 12um, a stripe coating film, the coating line width error range is 0 ~ 1.5mm, a double-coated film, bis the coated surface of the line width error range is 0 ~ 1.5mm, a resistive film is less than 30mΩ; (2) preparation of composite conductive base film, i.e., film B: B film of the activated carbon containing a weight ratio of 40 to 90%, conductive graphite containing a weight ratio of 2 to 50% by weight of a binder containing 2 to 25%; and XC-72 active carbon is GH-3892 in one or both in any mixing ratio, from the company Cabont; conductive graphite K56 is the AB-065M and one or two in any mixing ratio, from Timcal Graphite andCarbon company;?? a thermoplastic binder, may be 出加工成膜,粘合剂是乙烯-四氟乙烯共聚物;B膜是活性炭、导电石墨和粘合剂三种粉末料经过干粉混合均匀而成的混合粉末,干粉混合是在高速混合机中完成的;B膜是由三辊塑炼机制备的,三辊塑炼机的塑炼温度的温度范围是300~500℃,塑炼时间是10~120分钟,所制备的B膜的长度是1~2000米,厚度是50~500um;(3)干法热压制备电极材料:由A膜和B膜经加热压制而成,然后通过胶带分切机分条制成分条电极膜;(4)干法制备电极:在卷绕机上将两条相同尺寸的分条电极膜夹上隔离膜制备而成电极,卷绕机的芯子直径为5~200mm,卷绕的芯子高度为5~200mm;(5)将电极放入铝制超级电容壳内,盖上盖子,经过激光焊接接通电极的正负极,注进电解液,再封口便制成超级电容器。 The deposition process, the binder is an ethylene - tetrafluoroethylene copolymer; B is a film of activated carbon, conductive graphite, and a binder of the three powders were fed through a dry powder obtained by mixing uniformly mixed powder dry mixed in a high speed mixer completed; mastication temperature of the temperature range B film is composed of three-roll mill mechanism prepared, three-roll mill is 300 ~ 500 ℃, mastication time is 10 to 120 minutes, length B of the film prepared is 1 to 2000 m, a thickness of 50 ~ 500um; preparation of an electrode material (3) dry pressing: the pressing film by A and B formed by heating the film, and then slitting the tape by slitting a film was made in bar electrode; ( 4) preparation of dry electrode Method: core diameter in two points of the electrode films of the same size on a winder folder prepared by the electrode, separator winder is 5 ~ 200mm, a height of the winding cores 5 ~ 200mm; (5) the super capacitor electrode placed in an aluminum housing, cover, after turning on the laser welding of the positive and negative electrodes, an electrolyte injected into, then made reclosable supercapacitor.
  2. 2. 根据权利要求1所述的一种规模化生产的超级电容器工艺,其特征是:所述的涂布机的涂布速度为25〜55m/min。 The supercapacitor according to a process for large-scale production as claimed in claim 1, characterized in that: the coating speed of the coater was 25~55m / min.
  3. 3. 根据权利要求1或2所述的一种规模化生产的超级电容器工艺,其特征是:所述的A膜的涂布量是2. 8〜5. 2g/m、涂布厚度是6〜10um, A膜是条状涂布,涂布的线条宽度误差范围是0〜0. 5mm, A膜是双面涂布,双面涂布的线条宽度误差范围是0. 5mm。 3. According to a large-scale production process or supercapacitor according to claim 1, characterized in that: A coating amount of the film is 2. 8~5 2g / m, the coating thickness is 6. ~10um, a stripe coating film is a coating line width error range 0~0. 5mm, a double-sided coated film is coated on both sides of the line width error range 0. 5mm.
  4. 4. 根据权利要求1所述的一种规模化生产的超级电容器工艺,其特征是:所述的B膜含活性炭重量比60〜80%,导电石墨重量比10〜20%,粘合剂重量比10〜20%。 The supercapacitor according to a process for large-scale production as claimed in claim 1, wherein: said film containing B ratio of 60~80% by weight of activated carbon, conductive graphite weight ratio of 10-20%, by weight of the binder than 10-20%.
  5. 5. 根据权利要求1或4所述的一种规模化生产的超级电容器工艺,其特征是:所述的B 膜是由三辊塑炼机制备的,三辊塑炼机的塑炼温度的温度范围是320〜38(TC,塑炼时间是30〜40分钟,所制备的B膜的长度是1000〜2000米,厚度是100〜250um。 The supercapacitor or a process for large-scale production of 4 according to claim 1, characterized in that: the film is composed of three B-roll mill prepared mechanism, three-roll mill mastication temperature temperature range is 320~38 (TC, mastication time is 30 to 40 minutes, the length of the B film is prepared 1000~2000 m, thickness 100~250um.
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CN1317809A (en) 2000-04-12 2001-10-17 李永熙 Super-grade capacitor for electrode of using new material and its mfg. method
US6804108B2 (en) 2000-05-12 2004-10-12 Maxwell Electronics, Inc. Electrochemical double layer capacitor having carbon powder electrodes

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CN1317809A (en) 2000-04-12 2001-10-17 李永熙 Super-grade capacitor for electrode of using new material and its mfg. method
US6804108B2 (en) 2000-05-12 2004-10-12 Maxwell Electronics, Inc. Electrochemical double layer capacitor having carbon powder electrodes

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