WO2016095559A1 - Method for dispersing composite conductive agent in electrode slurry of lithium ion capacitor - Google Patents

Method for dispersing composite conductive agent in electrode slurry of lithium ion capacitor Download PDF

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WO2016095559A1
WO2016095559A1 PCT/CN2015/087919 CN2015087919W WO2016095559A1 WO 2016095559 A1 WO2016095559 A1 WO 2016095559A1 CN 2015087919 W CN2015087919 W CN 2015087919W WO 2016095559 A1 WO2016095559 A1 WO 2016095559A1
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conductive agent
carbon nanotubes
composite conductive
dispersing
lithium ion
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PCT/CN2015/087919
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French (fr)
Chinese (zh)
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阮殿波
黄�益
傅冠生
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宁波南车新能源科技有限公司
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Publication of WO2016095559A1 publication Critical patent/WO2016095559A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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 present invention relates to the field of supercapacitor technology, and in particular to a method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry.
  • Supercapacitors are widely used in the industry because of their high power, long service life and fast charging speed.
  • the electrode materials of conventional supercapacitor pads are usually made of carbon-based active materials (such as activated carbon) and binders. Defects with low voltage and low energy density are limited in many applications. Therefore, in order to increase the voltage and energy density of the supercapacitor, the existing supercapacitor electrode sheets are prepared by incorporating a lithium-containing material into the carbon-based active material.
  • the electronic conductivity of the lithium-containing material is relatively low. Therefore, it is necessary to add a conductive agent to improve the conductivity during the preparation of the electrode sheet slurry.
  • the commonly used conductive agents are mainly granular conductive carbon black, carbon fiber and the like.
  • the conventional slurry is prepared by adding an active material, a conductive agent, a binder and an organic solvent to a mixer or a dispersing machine at a certain ratio and stirring for a certain period of time to obtain a pole piece slurry.
  • conductive particles such as conductive carbon black are small, they are easily agglomerated and are difficult to disperse in an organic solvent.
  • a conductive polymer such as a single conductive carbon black or carbon fiber cannot be used to form a conductive network, and it is difficult to achieve a significant improvement in power. Performance needs. Therefore, in the preparation process of the lithium ion capacitor electrode slurry, how to select a suitable conductive agent and uniformly disperse the conductive agent is of great significance for improving the electrical performance of the lithium ion capacitor.
  • CN102496476A Chinese Patent Application Publication No. 2012.06.13 discloses a method for preparing a supercapacitor slurry, which specifically discloses an activated carbon, a conductive agent having an average particle diameter of 1 to 30 ⁇ m and a BET specific surface of 400 to 5000 m 2 /g.
  • the binder, solvent and grinding balls are ball-milled into a slurry for supercapacitor electrodes.
  • the preparation method comprises the following steps: the activated carbon, the conductive agent, the binder, the solvent and the grinding ball are ball-milled into a slurry for the supercapacitor electrode, and the disadvantage is that the conductive agent cannot be uniformly dispersed and wrapped in the electrode activity by ball milling.
  • the surface of the substance (ie, activated carbon), and the ball mill has low working efficiency; in addition, the conductive agent is one or more of acetylene black, conductive carbon black, conductive graphite and carbon fiber, and these carbon-based conductive agents are only embedded in the activated carbon. It does not form a good conductive network structure on the surface of activated carbon, and is conductive to the electrode sheets. The rate of improvement is limited.
  • the invention is to solve the problem that the conductive agent in the lithium ion capacitor electrode slurry of the prior art is not easy to disperse and cannot form the conductive network structure effectively, and provides a method for dispersing the composite conductive agent in the lithium ion capacitor electrode slurry.
  • the invention has simple process steps, strong operability, and is suitable for industrial production, and can uniformly disperse the composite conductive agent and form a three-dimensional conductive network structure, and the power performance is significantly improved while maintaining a high specific energy of the capacitor.
  • a method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry comprising the steps of:
  • the conductive agent is screened by the invention, wherein graphene, carbon nanotubes and conductive carbon black are used as conductive agents, wherein the conductive carbon black is a spherical structure, graphene is a single-layer sheet structure composed of carbon atoms, and the carbon nanotubes are mainly
  • the three conductive agents exhibit different structures for forming a plurality of layers of the carbon atoms arranged in a hexagonal shape to the tens of layers. When the three conductive agents are mixed and dispersed, the carbon is centered on the conductive carbon black.
  • the two ends of the nanotube are respectively connected to the adjacent conductive carbon black to connect different conductive carbon blacks in series to form a three-dimensional conductive network structure, and the graphene is wrapped on the surface of the conductive carbon black to form composite conductive particles to further improve the conductivity.
  • the electrical conductivity of the composite conductive agent of the present invention can be significantly improved compared to a single conductive agent or a conductive agent forming a planar conductive network; the surfactant can improve the surface infiltration of the carbon-based conductive agent in an organic solvent; Performance and dispersion.
  • Stepwise dispersion first, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed, followed by adding carbon nanotubes for the first high-speed dispersion, and finally adding graphene for the second high speed. Disperse it.
  • the invention firstly mixes the conductive carbon black with N-methylpyrrolidone and a surfactant, and then ultrasonically disperses to ensure that the conductive carbon black is sufficiently uniformly dispersed, and at the same time supplements the surfactant to improve the dispersion effect, and then sequentially adds carbon nanotubes and graphite.
  • the olefin is dispersed at a high speed to form a three-dimensional conductive network structure, and the step of adding the components is extremely important, otherwise a three-dimensional conductive network structure, ultrasonic dispersion and mechanical
  • the dispersion process steps are simple, low in cost, and easy to operate.
  • the conductive carbon black has a particle diameter of 10 to 50 nm.
  • the carbon nanotube has a diameter of 50 to 100 nm.
  • the carbon nanotubes are surface-treated carbon nanotubes, and the surface-treated carbon nanotubes are obtained by the following method:
  • the carbon nanotubes are added to chlorosulfonic acid, heated to 80-100 ° C for 1 to 3 hours, cooled, filtered, and the filtrate is washed with deionized water until the pH is neutral, and dried under vacuum to obtain swollen carbon nanotubes.
  • the chlorosulfonic acid can intercalate and swell the carbon nanotube bundle, and separate the carbon nanotubes from each other and expose the highly reactive amorphous carbon material on the surface thereof, thereby improving the dispersibility and facilitating the amorphous in the subsequent steps.
  • the carbon material is sufficiently removed to improve the performance of the carbon nanotubes.
  • the non-oxidizing acid (hydrochloric acid) pickling method further removes impurities to obtain pure carbon nanotubes.
  • the process conditions of the ultrasonic vibration are: power 4 to 6 W, and the oscillation time is 1 to 2 h.
  • prolonging the ultrasonic time will increase the dispersibility of the carbon nanotubes, but at the same time, the length of the carbon nanotubes will be shortened and the defects will be increased, thereby causing a decrease in the electrical conductivity when applied in a battery.
  • the conditions of the oscillation are critical.
  • the present invention strictly limits the conditions of the ultrasonic vibration, and improves the dispersibility of the carbon nanotubes under the premise of minimizing the damage to the length of the carbon nanotubes, and the obtained carbon nanotubes have high purity.
  • the surfactant is linolenic acid, cetyltrimethylammonium bromide, stearic acid, sodium lauryl sulfate or sodium dodecylbenzenesulfonate.
  • the surfactant is linolenic acid, cetyltrimethylammonium bromide, stearic acid, sodium lauryl sulfate or sodium dodecylbenzenesulfonate.
  • the surfactant is linolenic acid, cetyltrimethylammonium bromide, stearic acid, sodium lauryl sulfate or sodium dodecylbenzenesulfonate.
  • the process conditions of the ultrasonic dispersion are: a frequency of 15 to 20 KHz, a power of 200 to 300 W, and an ultrasonic time of 20 to 30 min.
  • the present invention performs ultrasonic dispersion time-breaking.
  • Hydrogen is introduced into the ground to roll the dispersed material from the bottom to the top to break the transverse standing wave formed by the ultrasonic wave in the dispersed material, so as to prevent the conductive carbon black from accumulating at the nodes, the hydrogen density is small, and the hydrogen will quickly escape after being introduced. Out, the effect is good.
  • the first high-speed dispersion and the second high-speed dispersion process parameters are: a rotation speed of 6000 to 10000 r/min, and a dispersion time of 30 to 60 minutes.
  • the first high-speed dispersion and the second high-speed dispersion are both carried out under vacuum.
  • Dispersion is carried out under vacuum to remove air bubbles and to avoid affecting the dispersion uniformity of the material.
  • the present invention has the following beneficial effects:
  • the conductive agent is screened, and graphene, carbon nanotubes and conductive carbon black are used as conductive agents, and the three cooperate to form a three-dimensional conductive network structure, which is beneficial to improving conductivity;
  • Step-by-step feeding dispersion firstly, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed for 20 min at a frequency of 15 kHz and a power of 200 W, and hydrogen is introduced into the liquid solution every 1 min during ultrasonic dispersion. Each time the hydrogen gas enters time is 5S, the amount of gas is 0.3m 3 /h, and then the carbon nanotubes are added for the first high-speed dispersion for 60 minutes under the condition of vacuum and rotation speed of 6000r/min, and finally graphene is added in vacuum and The second high-speed dispersion was carried out for 60 min under the condition of a rotational speed of 6000 r/min.
  • the conductive carbon black constitutes a composite conductive agent, and is also referred to as N-methylpyrrolidone of 9 times the mass of the composite conductive agent and a surfactant of 15% by mass of the composite conductive agent, and the surfactant is cetyl group.
  • Trimethylammonium bromide, stearic acid, and sodium lauryl sulfate are mixed at a mass ratio of 1:1:1.
  • the carbon nanotubes are surface-treated carbon nanotubes, which are obtained by the following methods:
  • Step-by-step feeding dispersion firstly, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed for 30 min at a frequency of 20 KHz and a power of 300 W, and hydrogen is introduced into the liquid solution every 3 minutes during ultrasonic dispersion.
  • the feed rate is 0.5m 3 /h
  • the carbon nanotubes are added for the first high-speed dispersion for 30min under the condition of vacuum and rotation speed of 10000r/min
  • graphene is added in vacuum and
  • the second high-speed dispersion was carried out for 30 min under the condition of a rotational speed of 10,000 r/min.
  • the carbon black constitutes a composite conductive agent, and is also referred to as N-methylpyrrolidone of 7 times the mass of the composite conductive agent and a surfactant of 10% by mass of the composite conductive agent, and the surfactant is linolenic acid, 16
  • One or more of alkyltrimethylammonium bromide, stearic acid, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and the carbon nanotubes are surface-treated carbon nanotubes, which pass The following methods are made:
  • Step-by-step feeding dispersion firstly, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed for 25 minutes at a frequency of 18 kHz and a power of 250 W, and hydrogen is introduced into the liquid solution every 2 minutes during ultrasonic dispersion.
  • the hydrogen gas inlet time is 8S
  • the amount of gas is 0.4m 3 /h
  • the carbon nanotubes are added for the first high-speed dispersion for 40 minutes under the condition of vacuum and rotation speed of 8000r/min
  • graphene is added in vacuum and
  • the second high-speed dispersion was carried out for 40 min under the condition of a rotational speed of 8000 r/min.
  • the invention optimizes the formulation of the conductive agent and improves the feeding step and the dispersion mode, the conductive agent has good dispersion effect, and can form a three-dimensional conductive network structure, which is beneficial to improving the conductivity of the super capacitor, and has simple process steps and operability. Strong, suitable for industrial production, has broad application prospects.

Abstract

Disclosed is a method for dispersing a composite conductive agent in an electrode slurry of a lithium ion capacitor, comprising the following steps: (1) material weighing: each component is weighed according to the proportions: 0.5-14.5% of graphene, 5.5-14.5% of carbon nanotubes, and the balance being conductive carbon black, wherein the graphene, carbon nanotubes and conductive carbon black form the composite conductive agent; at the same time, N-methylpyrrolidone in an amount of 4-9 times the mass of the composite conductive agent and a surfactant in an amount of 5-15% of the mass of the composite conductive agent are weighed, for use; and (2) stepwise charging and dispersing: the conductive carbon black is firstly mixed with the N-methylpyrrolidone and the surfactant and thereafter subjected to ultrasonic dispersion, subsequently, the carbon nanotubes are added for a first high speed dispersion, and finally, the graphene is added for a second high speed dispersion. The process steps of the present invention are simple, strong in operability, and suitable for industrial productions, and can make the composite conductive agent be uniformly dispersed to form a three-dimensional conductive network structure, and while a higher specific energy of the capacitor is maintained, the power performance is significantly improved.

Description

一种锂离子电容器电极浆料中复合导电剂的分散方法Method for dispersing composite conductive agent in lithium ion capacitor electrode slurry 技术领域Technical field
本发明涉及超级电容器技术领域，尤其是涉及一种锂离子电容器电极浆料中复合导电剂的分散方法。The present invention relates to the field of supercapacitor technology, and in particular to a method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry.
背景技术Background technique
超级电容器因其具有功率高、使用寿命长和充电速度快等优点而被业界广泛关注，但常规超级电容器电极片的电极材料通常由碳基活性材料(如活性炭)和粘结剂制成，存在电压低、能量密度低的缺陷，在很多方面的应用都受到了限制。因此，为提高超级电容器的电压和能量密度，现有的超级电容器电极片在制备时会在碳基活性材料中掺入含锂材料。Supercapacitors are widely used in the industry because of their high power, long service life and fast charging speed. However, the electrode materials of conventional supercapacitor pads are usually made of carbon-based active materials (such as activated carbon) and binders. Defects with low voltage and low energy density are limited in many applications. Therefore, in order to increase the voltage and energy density of the supercapacitor, the existing supercapacitor electrode sheets are prepared by incorporating a lithium-containing material into the carbon-based active material.
但是含锂材料的电子电导率都比较低，因此在电极片浆料的制备过程中需要加入导电剂改善其导电性，常用的导电剂主要为颗粒状的导电炭黑、碳纤维等。传统的浆料的制备方法为：将活性材料、导电剂、粘结剂和有机溶剂按照一定配比同时加入搅拌机或者分散机中进行搅拌一定时间后，即得极片浆料。However, the electronic conductivity of the lithium-containing material is relatively low. Therefore, it is necessary to add a conductive agent to improve the conductivity during the preparation of the electrode sheet slurry. The commonly used conductive agents are mainly granular conductive carbon black, carbon fiber and the like. The conventional slurry is prepared by adding an active material, a conductive agent, a binder and an organic solvent to a mixer or a dispersing machine at a certain ratio and stirring for a certain period of time to obtain a pole piece slurry.
然而由于导电炭黑等导电剂颗粒小，很容易团聚，很难在有机溶剂中分散，另外，使用单一的导电炭黑或者碳纤维等导电剂不能很好的构成导电网络，很难达到大幅改善功率性能的需要。因此，在锂离子电容器电极浆料的制备过程中，如何选择合适的导电剂并使导电剂均匀分散，对于提高锂离子电容器的电性能具有重要意义。However, since conductive particles such as conductive carbon black are small, they are easily agglomerated and are difficult to disperse in an organic solvent. In addition, a conductive polymer such as a single conductive carbon black or carbon fiber cannot be used to form a conductive network, and it is difficult to achieve a significant improvement in power. Performance needs. Therefore, in the preparation process of the lithium ion capacitor electrode slurry, how to select a suitable conductive agent and uniformly disperse the conductive agent is of great significance for improving the electrical performance of the lithium ion capacitor.
CN102496476A，申请公布日2012.06.13的中国专利公开了一种超级电容器浆料制备方法，具体公开了：将平均粒径1～30微米，BET比表面为400～5000m2/g的活性炭、导电剂、粘结剂、溶剂和磨球放入球磨罐中球磨成超级电容器电极用浆料。该制备方法将活性炭、导电剂、粘结剂、溶剂和磨球放入球磨罐中球磨成超级电容器电极用浆料，其不足之处在于：通过球磨导电剂并不能均匀分散并包裹在电极活性物质(即活性炭)的表面，且球磨的工作效率低；另外导电剂为乙炔黑、导电碳黑、导电石墨和碳纤维中的一种或几种，这些碳基导电剂只是镶嵌在活性炭之间，并不能在活性炭表面形成良好的导电网络结构，对于电极片导电 率的提高效果有限。CN102496476A, Chinese Patent Application Publication No. 2012.06.13 discloses a method for preparing a supercapacitor slurry, which specifically discloses an activated carbon, a conductive agent having an average particle diameter of 1 to 30 μm and a BET specific surface of 400 to 5000 m 2 /g. The binder, solvent and grinding balls are ball-milled into a slurry for supercapacitor electrodes. The preparation method comprises the following steps: the activated carbon, the conductive agent, the binder, the solvent and the grinding ball are ball-milled into a slurry for the supercapacitor electrode, and the disadvantage is that the conductive agent cannot be uniformly dispersed and wrapped in the electrode activity by ball milling. The surface of the substance (ie, activated carbon), and the ball mill has low working efficiency; in addition, the conductive agent is one or more of acetylene black, conductive carbon black, conductive graphite and carbon fiber, and these carbon-based conductive agents are only embedded in the activated carbon. It does not form a good conductive network structure on the surface of activated carbon, and is conductive to the electrode sheets. The rate of improvement is limited.
发明内容Summary of the invention
本发明是为了解决现有技术的锂离子电容器电极浆料中的导电剂不易分散，不能有效形成导电网络结构的问题，提供了一种锂离子电容器电极浆料中复合导电剂的分散方法，本发明工艺步骤简单，可操作性强，适合工业化生产，能使复合导电剂均匀分散并形成立体的导电网络结构，在保持电容较高比能量的同时，功率性能得到显著改善。The invention is to solve the problem that the conductive agent in the lithium ion capacitor electrode slurry of the prior art is not easy to disperse and cannot form the conductive network structure effectively, and provides a method for dispersing the composite conductive agent in the lithium ion capacitor electrode slurry. The invention has simple process steps, strong operability, and is suitable for industrial production, and can uniformly disperse the composite conductive agent and form a three-dimensional conductive network structure, and the power performance is significantly improved while maintaining a high specific energy of the capacitor.
为了实现上述目的，本发明采用以下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种锂离子电容器电极浆料中复合导电剂的分散方法，包括以下步骤：A method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry, comprising the steps of:
(1)称料：按0.5～14.5％石墨烯，5.5～14.5％碳纳米管，余量为导电碳黑的配比称取各组分，其中石墨烯、碳纳米管和导电碳黑构成复合导电剂，同时称取为复合导电剂质量4～9倍量的N-甲基吡咯烷酮和为复合导电剂质量5～15％的表面活性剂，待用。本发明对导电剂进行了筛选，以石墨烯、碳纳米管和导电碳黑作为导电剂，其中导电炭黑为球体结构，石墨烯为由碳原子构成的单层片状结构，碳纳米管主要为由呈六边形排列的碳原子构成数层到数十层的同轴圆管结构，三种导电剂呈现不同的结构，当三种导电剂混合分散时，以导电炭黑为中心，碳纳米管的两端分别连接相邻的导电炭黑上从而将不同的导电炭黑串接起来形成立体的导电网络结构，石墨烯则会包裹在导电碳黑表面形成复合导电颗粒以进一步提高导电率，本发明复合导电剂的导电率相比单一的导电剂或者形成平面状导电网络的导电剂相比，导电率能得到明显改善；表面活性剂可以改善碳基导电剂在有机溶剂中的表面浸润性能和分散效果。(1) Weighing: Weigh the components according to the ratio of 0.5 to 14.5% graphene and 5.5 to 14.5% carbon nanotubes, and balance the amount of conductive carbon black. The graphene, carbon nanotubes and conductive carbon black are combined. The conductive agent is also weighed as N-methylpyrrolidone in an amount of 4 to 9 times the mass of the composite conductive agent and a surfactant of 5 to 15% by mass of the composite conductive agent, and is used. The conductive agent is screened by the invention, wherein graphene, carbon nanotubes and conductive carbon black are used as conductive agents, wherein the conductive carbon black is a spherical structure, graphene is a single-layer sheet structure composed of carbon atoms, and the carbon nanotubes are mainly The three conductive agents exhibit different structures for forming a plurality of layers of the carbon atoms arranged in a hexagonal shape to the tens of layers. When the three conductive agents are mixed and dispersed, the carbon is centered on the conductive carbon black. The two ends of the nanotube are respectively connected to the adjacent conductive carbon black to connect different conductive carbon blacks in series to form a three-dimensional conductive network structure, and the graphene is wrapped on the surface of the conductive carbon black to form composite conductive particles to further improve the conductivity. The electrical conductivity of the composite conductive agent of the present invention can be significantly improved compared to a single conductive agent or a conductive agent forming a planar conductive network; the surfactant can improve the surface infiltration of the carbon-based conductive agent in an organic solvent; Performance and dispersion.
(2)分步加料分散：先将导电炭黑与N-甲基吡咯烷酮、表面活性剂混合后进行超声分散，接着加入碳纳米管进行第一次高速分散，最后加入石墨烯进行第二次高速分散即可。本发明先将导电炭黑与N-甲基吡咯烷酮、表面活性剂混合后进行超声分散以保证导电碳黑充分均匀分散，同时辅以表面活性剂以提高分散效果，再依次加入碳纳米管、石墨烯进行高速分散以形成立体的导电网络结构，各组分的加入步骤极为重要，否则得不到立体的导电网络结构，超声分散与机械 分散工艺步骤简单，成本低，且易操作。(2) Stepwise dispersion: first, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed, followed by adding carbon nanotubes for the first high-speed dispersion, and finally adding graphene for the second high speed. Disperse it. The invention firstly mixes the conductive carbon black with N-methylpyrrolidone and a surfactant, and then ultrasonically disperses to ensure that the conductive carbon black is sufficiently uniformly dispersed, and at the same time supplements the surfactant to improve the dispersion effect, and then sequentially adds carbon nanotubes and graphite. The olefin is dispersed at a high speed to form a three-dimensional conductive network structure, and the step of adding the components is extremely important, otherwise a three-dimensional conductive network structure, ultrasonic dispersion and mechanical The dispersion process steps are simple, low in cost, and easy to operate.
作为优选，步骤(1)中，所述导电碳黑的粒径10～50nm。Preferably, in the step (1), the conductive carbon black has a particle diameter of 10 to 50 nm.
作为优选，步骤(1)中，所述碳纳米管管径为50～100nm。Preferably, in the step (1), the carbon nanotube has a diameter of 50 to 100 nm.
作为优选，所述碳纳米管为经表面处理的碳纳米管，经表面处理的碳纳米管通过以下方法制得：Preferably, the carbon nanotubes are surface-treated carbon nanotubes, and the surface-treated carbon nanotubes are obtained by the following method:
(a)将碳纳米管加入氯磺酸中，加热至80～100℃溶胀1～3h，冷却，过滤，将过滤物用去离子水洗至pH呈中性，真空干燥，得溶胀碳纳米管。氯磺酸能够插层、溶胀碳纳米管束，使碳纳米管彼此分开并将其表面高反应活性的非晶碳物质暴露出来，既能提高其分散性，又有利于后续步骤中将这些非晶碳物质充分去除，以提高碳纳米管的性能。(a) The carbon nanotubes are added to chlorosulfonic acid, heated to 80-100 ° C for 1 to 3 hours, cooled, filtered, and the filtrate is washed with deionized water until the pH is neutral, and dried under vacuum to obtain swollen carbon nanotubes. The chlorosulfonic acid can intercalate and swell the carbon nanotube bundle, and separate the carbon nanotubes from each other and expose the highly reactive amorphous carbon material on the surface thereof, thereby improving the dispersibility and facilitating the amorphous in the subsequent steps. The carbon material is sufficiently removed to improve the performance of the carbon nanotubes.
(b)将溶胀碳纳米管加入质量分数为1～2％的十二烷基硫酸钠乙醇溶液中，于80～90℃条件下搅拌30～60min，抽滤，烘干，得改性碳纳米管。通过十二烷基硫酸钠对溶胀碳纳米管进行改性，十二烷基硫酸钠上的链式烷基可通过疏水作用吸附在碳纳米管表面，十二烷基硫酸钠上的硫酸根增加了碳纳米管表面的负电量，增加了碳纳米管间的静电排斥力，从而提高碳纳米管在浆料中的稳定性，能有效避免碳纳米管发生团聚。(b) adding the swollen carbon nanotubes to a sodium dodecyl sulfate ethanol solution having a mass fraction of 1 to 2%, stirring at 80 to 90 ° C for 30 to 60 minutes, suction filtration, and drying to obtain a modified carbon nanoparticle. tube. The swollen carbon nanotubes are modified by sodium lauryl sulfate, and the chain alkyl group on sodium lauryl sulfate can be adsorbed on the surface of the carbon nanotube by hydrophobic action, and the sulfate on the sodium lauryl sulfate is increased. The negative charge of the surface of the carbon nanotubes increases the electrostatic repulsion between the carbon nanotubes, thereby improving the stability of the carbon nanotubes in the slurry, and effectively avoiding agglomeration of the carbon nanotubes.
(c)将改性碳纳米管边搅拌边加入30～40％的过氧化氢溶液中，于60～80℃恒温加热8～10h，抽滤，将过滤物用去离子水洗至pH呈中性后转移至3～4mol/L的盐酸溶液中，超声振荡4～8h，抽滤，将过滤物用去离子水洗至pH呈中性，真空烘干，即得经表面处理的碳纳米管。利用氧化氢的强氧化性对碳纳米管中的非晶碳物质进行氧化除杂，在除杂的同时不仅保持了碳纳米管结构的完整性，还可提高碳纳米管的收率，并结合非氧化酸(盐酸)酸洗的方法进一步除杂，从而以获得纯净的碳纳米管。(c) adding the modified carbon nanotubes to a 30-40% hydrogen peroxide solution while stirring, heating at 60-80 ° C for 8-10 h, suction filtration, washing the filtrate with deionized water until the pH is neutral. After that, the solution was transferred to a 3 to 4 mol/L hydrochloric acid solution, ultrasonically shaken for 4 to 8 hours, and suction filtered, and the filtrate was washed with deionized water until the pH was neutral, and vacuum-dried to obtain surface-treated carbon nanotubes. Oxidation and impurity removal of amorphous carbon materials in carbon nanotubes by the strong oxidizing property of hydrogen peroxide, not only maintaining the integrity of the carbon nanotube structure, but also improving the yield of carbon nanotubes, and combining The non-oxidizing acid (hydrochloric acid) pickling method further removes impurities to obtain pure carbon nanotubes.
作为优选，步骤(c)中，超声振荡的工艺条件为：功率4～6W，振荡时间1～2h。在一定的超声功率下，延长超声时间会提高碳纳米管的分散性，但同时亦会剪短碳纳米管长度并使其缺陷增加，从而造成其在电池中应用时导电性能的降低，因此超声振荡的条件十分关键，本发明严格限定超声振荡的条件，在尽可能减小对碳纳米管长度的破坏的前提下，提高碳纳米管的分散性，而且得到的碳纳米管纯度高。 Preferably, in the step (c), the process conditions of the ultrasonic vibration are: power 4 to 6 W, and the oscillation time is 1 to 2 h. At a certain ultrasonic power, prolonging the ultrasonic time will increase the dispersibility of the carbon nanotubes, but at the same time, the length of the carbon nanotubes will be shortened and the defects will be increased, thereby causing a decrease in the electrical conductivity when applied in a battery. The conditions of the oscillation are critical. The present invention strictly limits the conditions of the ultrasonic vibration, and improves the dispersibility of the carbon nanotubes under the premise of minimizing the damage to the length of the carbon nanotubes, and the obtained carbon nanotubes have high purity.
作为优选，步骤(1)中，所述表面活性剂为亚麻酸、十六烷基三甲基溴化铵、硬脂酸、十二烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种。Preferably, in the step (1), the surfactant is linolenic acid, cetyltrimethylammonium bromide, stearic acid, sodium lauryl sulfate or sodium dodecylbenzenesulfonate. One or more.
作为优选，步骤(2)中，超声分散的工艺条件为：频率15～20KHz，功率200～300W，超声时间20～30min。Preferably, in the step (2), the process conditions of the ultrasonic dispersion are: a frequency of 15 to 20 KHz, a power of 200 to 300 W, and an ultrasonic time of 20 to 30 min.
作为优选，超声分散期间每隔1～3min向料液中通入氢气，每次氢气通入时间5～10S，通入量为0.3～0.5m3/h。超声分散时超声波会在分散物料中形成驻波，使得导电炭黑会受机械力的作用而聚集在波节处，不利于进一步分散，为解决这一问题，本发明在进行超声分散时间断性地通入氢气以使有分散物料从下向上翻滚，破坏超声波在分散物料中所形成的横向的驻波，避免导电碳黑在在波节处发生聚集，氢气密度小，通入后会迅速逸出，使用效果好。Preferably, hydrogen is introduced into the feed liquid every 1 to 3 minutes during the ultrasonic dispersion, and the hydrogen permeation time is 5 to 10 seconds, and the permeation amount is 0.3 to 0.5 m 3 /h. Ultrasonic dispersion will form a standing wave in the dispersed material, so that the conductive carbon black will be concentrated at the nodes by mechanical force, which is not conducive to further dispersion. To solve this problem, the present invention performs ultrasonic dispersion time-breaking. Hydrogen is introduced into the ground to roll the dispersed material from the bottom to the top to break the transverse standing wave formed by the ultrasonic wave in the dispersed material, so as to prevent the conductive carbon black from accumulating at the nodes, the hydrogen density is small, and the hydrogen will quickly escape after being introduced. Out, the effect is good.
作为优选，步骤(2)中，第一次高速分散与第二次高速分散的工艺参数为：转速为6000～10000r/min，分散时间为30～60min。Preferably, in the step (2), the first high-speed dispersion and the second high-speed dispersion process parameters are: a rotation speed of 6000 to 10000 r/min, and a dispersion time of 30 to 60 minutes.
作为优选，步骤(2)中，第一次高速分散与第二次高速分散均在真空条件下进行。在真空条件下进行分散以去除气泡，避免影响物料的分散均匀性。Preferably, in the step (2), the first high-speed dispersion and the second high-speed dispersion are both carried out under vacuum. Dispersion is carried out under vacuum to remove air bubbles and to avoid affecting the dispersion uniformity of the material.
因此，本发明具有如下有益效果：Therefore, the present invention has the following beneficial effects:
(1)对导电剂进行了筛选，以石墨烯、碳纳米管和导电碳黑作为导电剂，三者协同配合以形成立体的导电网络结构，有利于改善导电率；(1) The conductive agent is screened, and graphene, carbon nanotubes and conductive carbon black are used as conductive agents, and the three cooperate to form a three-dimensional conductive network structure, which is beneficial to improving conductivity;
(2)对加料步骤和分散方式进行了改进，分散效果好，工艺步骤简单，可操作性强，适合工业化生产。(2) The feeding step and the dispersion method are improved, the dispersion effect is good, the process steps are simple, the operability is strong, and it is suitable for industrial production.
具体实施方式detailed description
下面通过具体实施方式对本发明做进一步的描述。The invention is further described below by way of specific embodiments.
在本发明中，若非特指，所有百分比均为重量单位，所有设备和原料均可从市场购得或是本行业常用的，下述实施例中的方法，如无特别说明，均为本领域常规方法。In the present invention, unless otherwise specified, all percentages are by weight, all equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples, unless otherwise specified, are in the field. normal method.
实施例1Example 1
(1)称料：按0.5％石墨烯，5.5％管径为50nm的碳纳米管，余量为粒径10nm 的导电碳黑的配比称取各组分，其中石墨烯、碳纳米管和导电碳黑构成复合导电剂，同时称取为复合导电剂质量4倍量的N-甲基吡咯烷酮和为复合导电剂质量5％的表面活性剂，待用，其中表面活性剂为亚麻酸，碳纳米管为经表面处理的碳纳米管，其通过以下方法制得：(1) Weighing: 0.5% graphene, 5.5% carbon nanotubes with a diameter of 50 nm, the balance is 10 nm The composition of the conductive carbon black is weighed into various components, wherein the graphene, the carbon nanotubes and the conductive carbon black constitute a composite conductive agent, and the N-methylpyrrolidone of the composite conductive agent is weighed four times and is a composite conductive material. A surfactant of 5% by mass of surfactant, which is used as a surfactant, wherein the surfactant is linolenic acid, and the carbon nanotube is a surface-treated carbon nanotube, which is obtained by the following method:
(a)将碳纳米管加入氯磺酸中，加热至80℃溶胀1h，冷却，过滤，将过滤物用去离子水洗至pH呈中性，真空干燥，得溶胀碳纳米管；(a) adding carbon nanotubes to chlorosulfonic acid, heating to 80 ° C for 1 h, cooling, filtering, washing the filtrate with deionized water until the pH is neutral, vacuum drying, to obtain swollen carbon nanotubes;
(b)将溶胀碳纳米管加入质量分数为1％的十二烷基硫酸钠乙醇溶液中，于80℃条件下搅拌30min，抽滤，烘干，得改性碳纳米管；(b) adding the swollen carbon nanotubes to a sodium dodecyl sulfate ethanol solution having a mass fraction of 1%, stirring at 80 ° C for 30 min, suction filtration, and drying to obtain modified carbon nanotubes;
(c)将改性碳纳米管边搅拌边加入30％的过氧化氢溶液中，于60℃恒温加热8h，抽滤，将过滤物用去离子水洗至pH呈中性后转移至3mol/L的盐酸溶液中，超声振荡4h，抽滤，将过滤物用去离子水洗至pH呈中性，真空烘干，即得经表面处理的碳纳米管。(c) Adding the modified carbon nanotubes to a 30% hydrogen peroxide solution while stirring, heating at 60 ° C for 8 h, suction filtration, washing the filtrate with deionized water until the pH is neutral, and transferring to 3 mol/L. In the hydrochloric acid solution, ultrasonically shake for 4 h, suction filtration, the filtrate is washed with deionized water until the pH is neutral, and vacuum-dried to obtain surface-treated carbon nanotubes.
(2)分步加料分散：先将导电炭黑与N-甲基吡咯烷酮、表面活性剂混合后在频率15KHz，功率200W条件下超声分散20min，超声分散期间每隔1min向料液中通入氢气，每次氢气通入时间5S，通入量为0.3m3/h，接着加入碳纳米管在真空和转速为6000r/min的条件下进行第一次高速分散60min，最后加入石墨烯在真空和转速为6000r/min的条件下进行第二次高速分散60min。(2) Step-by-step feeding dispersion: firstly, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed for 20 min at a frequency of 15 kHz and a power of 200 W, and hydrogen is introduced into the liquid solution every 1 min during ultrasonic dispersion. Each time the hydrogen gas enters time is 5S, the amount of gas is 0.3m 3 /h, and then the carbon nanotubes are added for the first high-speed dispersion for 60 minutes under the condition of vacuum and rotation speed of 6000r/min, and finally graphene is added in vacuum and The second high-speed dispersion was carried out for 60 min under the condition of a rotational speed of 6000 r/min.
实施例2Example 2
(1)称料：按14.5％石墨烯，14.5％管径为100nm的碳纳米管，余量为粒径50nm的导电碳黑的配比称取各组分，其中石墨烯、碳纳米管和导电碳黑构成复合导电剂，同时称取为复合导电剂质量9倍量的N-甲基吡咯烷酮和为复合导电剂质量15％的表面活性剂，待用，其中表面活性剂为十六烷基三甲基溴化铵、硬脂酸、十二烷基硫酸钠按质量比1：1：1混合而成，碳纳米管为经表面处理的碳纳米管，其通过以下方法制得：(1) Weighing: According to 14.5% graphene, 14.5% carbon nanotubes with a diameter of 100 nm, and the balance of conductive carbon black with a particle size of 50 nm, weigh the components, among which graphene, carbon nanotubes and The conductive carbon black constitutes a composite conductive agent, and is also referred to as N-methylpyrrolidone of 9 times the mass of the composite conductive agent and a surfactant of 15% by mass of the composite conductive agent, and the surfactant is cetyl group. Trimethylammonium bromide, stearic acid, and sodium lauryl sulfate are mixed at a mass ratio of 1:1:1. The carbon nanotubes are surface-treated carbon nanotubes, which are obtained by the following methods:
(a)将碳纳米管加入氯磺酸中，加热至90℃溶胀2h，冷却，过滤，将过滤物用去离子水洗至pH呈中性，真空干燥，得溶胀碳纳米管；(a) adding carbon nanotubes to chlorosulfonic acid, heating to 90 ° C for 2 h, cooling, filtering, washing the filtrate with deionized water until the pH is neutral, vacuum drying, to obtain swollen carbon nanotubes;
(b)将溶胀碳纳米管加入质量分数为1～2％的十二烷基硫酸钠乙醇溶液中，于85℃条件下搅拌40min，抽滤，烘干，得改性碳纳米管； (b) adding the swollen carbon nanotubes to a sodium dodecyl sulfate ethanol solution having a mass fraction of 1 to 2%, stirring at 85 ° C for 40 min, suction filtration, and drying to obtain modified carbon nanotubes;
(c)将改性碳纳米管边搅拌边加入35％的过氧化氢溶液中，于70℃恒温加热9h，抽滤，将过滤物用去离子水洗至pH呈中性后转移至3.5mol/L的盐酸溶液中，超声振荡5h，抽滤，将过滤物用去离子水洗至pH呈中性，真空烘干，即得经表面处理的碳纳米管。(c) The modified carbon nanotubes were added to a 35% hydrogen peroxide solution while stirring, heated at 70 ° C for 9 h, suction filtered, and the filtrate was washed with deionized water until the pH was neutral and then transferred to 3.5 mol/ In the hydrochloric acid solution of L, ultrasonically shake for 5 h, suction filtration, and the filtrate is washed with deionized water until the pH is neutral, and vacuum-dried to obtain surface-treated carbon nanotubes.
(2)分步加料分散：先将导电炭黑与N-甲基吡咯烷酮、表面活性剂混合后在频率20KHz，功率300W条件下超声分散30min，超声分散期间每隔3min向料液中通入氢气，每次氢气通入时间10S，通入量为0.5m3/h，接着加入碳纳米管在真空和转速为10000r/min的条件下进行第一次高速分散30min，最后加入石墨烯在真空和转速为10000r/min的条件下进行第二次高速分散30min。(2) Step-by-step feeding dispersion: firstly, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed for 30 min at a frequency of 20 KHz and a power of 300 W, and hydrogen is introduced into the liquid solution every 3 minutes during ultrasonic dispersion. Each time the hydrogen gas enters time is 10S, the feed rate is 0.5m 3 /h, then the carbon nanotubes are added for the first high-speed dispersion for 30min under the condition of vacuum and rotation speed of 10000r/min, and finally graphene is added in vacuum and The second high-speed dispersion was carried out for 30 min under the condition of a rotational speed of 10,000 r/min.
实施例3Example 3
(1)称料：按10％石墨烯，12％管径为60nm的碳纳米管，余量为粒径20nm的导电碳黑配比称取各组分，其中石墨烯、碳纳米管和导电碳黑构成复合导电剂，同时称取为复合导电剂质量7倍量的N-甲基吡咯烷酮和为复合导电剂质量10％的表面活性剂，待用，其中表面活性剂为亚麻酸、十六烷基三甲基溴化铵、硬脂酸、十二烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种，碳纳米管为经表面处理的碳纳米管，其通过以下方法制得：(1) Weighing: According to 10% graphene, 12% carbon nanotubes with a diameter of 60nm, and the balance of conductive carbon black with a particle size of 20nm, weigh the components, including graphene, carbon nanotubes and conductive The carbon black constitutes a composite conductive agent, and is also referred to as N-methylpyrrolidone of 7 times the mass of the composite conductive agent and a surfactant of 10% by mass of the composite conductive agent, and the surfactant is linolenic acid, 16 One or more of alkyltrimethylammonium bromide, stearic acid, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and the carbon nanotubes are surface-treated carbon nanotubes, which pass The following methods are made:
(a)将碳纳米管加入氯磺酸中，加热至100℃溶胀3h，冷却，过滤，将过滤物用去离子水洗至pH呈中性，真空干燥，得溶胀碳纳米管；(a) adding carbon nanotubes to chlorosulfonic acid, heating to 100 ° C for 3 h, cooling, filtering, washing the filtrate with deionized water until the pH is neutral, vacuum drying, to obtain swollen carbon nanotubes;
(b)将溶胀碳纳米管加入质量分数为2％的十二烷基硫酸钠乙醇溶液中，于90℃条件下搅拌60min，抽滤，烘干，得改性碳纳米管；(b) adding the swollen carbon nanotubes to a mass fraction of 2% sodium dodecyl sulfate ethanol solution, stirring at 90 ° C for 60 min, suction filtration, drying to obtain modified carbon nanotubes;
(c)将改性碳纳米管边搅拌边加入40％的过氧化氢溶液中，于80℃恒温加热10h，抽滤，将过滤物用去离子水洗至pH呈中性后转移至4mol/L的盐酸溶液中，超声振荡8h，抽滤，将过滤物用去离子水洗至pH呈中性，真空烘干，即得经表面处理的碳纳米管。(c) The modified carbon nanotubes were added to a 40% hydrogen peroxide solution while stirring, heated at 80 ° C for 10 h, suction filtered, and the filtrate was washed with deionized water until the pH was neutral and then transferred to 4 mol/L. In the hydrochloric acid solution, ultrasonically shake for 8 h, suction filtration, the filtrate is washed with deionized water until the pH is neutral, and vacuum-dried to obtain surface-treated carbon nanotubes.
(2)分步加料分散：先将导电炭黑与N-甲基吡咯烷酮、表面活性剂混合后在频率18KHz，功率250W条件下超声分散25min，超声分散期间每隔2min向料液中通入氢气，每次氢气通入时间8S，通入量为0.4m3/h，接着加入碳纳米管在真空和转速为8000r/min的条件下进行第一次高速分散40min，最后加入石墨 烯在真空和转速为8000r/min的条件下进行第二次高速分散40min。(2) Step-by-step feeding dispersion: firstly, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed for 25 minutes at a frequency of 18 kHz and a power of 250 W, and hydrogen is introduced into the liquid solution every 2 minutes during ultrasonic dispersion. Each time the hydrogen gas inlet time is 8S, the amount of gas is 0.4m 3 /h, then the carbon nanotubes are added for the first high-speed dispersion for 40 minutes under the condition of vacuum and rotation speed of 8000r/min, and finally graphene is added in vacuum and The second high-speed dispersion was carried out for 40 min under the condition of a rotational speed of 8000 r/min.
本发明通过对导电剂配方的优化以及对加料步骤和分散方式的改进，导电剂分散效果好，并能形成立体的导电网络结构，有利于改善超级电容的导电率，工艺步骤简单，可操作性强，适合工业化生产，具有广阔的应用前景。The invention optimizes the formulation of the conductive agent and improves the feeding step and the dispersion mode, the conductive agent has good dispersion effect, and can form a three-dimensional conductive network structure, which is beneficial to improving the conductivity of the super capacitor, and has simple process steps and operability. Strong, suitable for industrial production, has broad application prospects.
以上所述的实施例只是本发明的一种较佳的方案，并非对本发明作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。 The above-mentioned embodiments are only a preferred embodiment of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications are possible without departing from the technical solutions described in the claims.

Claims (10)

  1. 一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，包括以下步骤：A method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry, comprising the steps of:
    (1)称料：按0.5～14.5％石墨烯，5.5～14.5％碳纳米管，余量为导电碳黑的配比称取各组分，其中石墨烯、碳纳米管和导电碳黑构成复合导电剂，同时称取为复合导电剂质量4～9倍量的N-甲基吡咯烷酮和为复合导电剂质量5～15％的表面活性剂，待用；(1) Weighing: Weigh the components according to the ratio of 0.5 to 14.5% graphene and 5.5 to 14.5% carbon nanotubes, and balance the amount of conductive carbon black. The graphene, carbon nanotubes and conductive carbon black are combined. The conductive agent is also weighed as N-methylpyrrolidone in an amount of 4 to 9 times the mass of the composite conductive agent and a surfactant of 5 to 15% by mass of the composite conductive agent, and is used;
    (2)分步加料分散：先将导电炭黑与N-甲基吡咯烷酮、表面活性剂混合后进行超声分散，接着加入碳纳米管进行第一次高速分散，最后加入石墨烯进行第二次高速分散即可。(2) Stepwise dispersion: first, the conductive carbon black is mixed with N-methylpyrrolidone and surfactant, and then ultrasonically dispersed, followed by adding carbon nanotubes for the first high-speed dispersion, and finally adding graphene for the second high speed. Disperse it.
  2. 根据权利要求1所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，步骤(1)中，所述导电碳黑的粒径10～50nm。The method of dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 1, wherein in the step (1), the conductive carbon black has a particle diameter of 10 to 50 nm.
  3. 根据权利要求1所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，步骤(1)中，所述碳纳米管管径为50～100nm。The method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 1, wherein in the step (1), the carbon nanotube has a diameter of 50 to 100 nm.
  4. 根据权利要求1或3所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，所述碳纳米管为经表面处理的碳纳米管，经表面处理的碳纳米管通过以下方法制得：The method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 1 or 3, wherein the carbon nanotube is a surface-treated carbon nanotube, and the surface-treated carbon nanotube Made by the following methods:
    (a)将碳纳米管加入氯磺酸中，加热至80～100℃溶胀1～3h，冷却，过滤，将过滤物用去离子水洗至pH呈中性，真空干燥，得溶胀碳纳米管；(a) adding carbon nanotubes to chlorosulfonic acid, heating to 80 ~ 100 ° C for 1 ~ 3h, cooling, filtering, the filtrate is washed with deionized water until the pH is neutral, vacuum drying, to obtain swollen carbon nanotubes;
    (b)将溶胀碳纳米管加入质量分数为1～2％的十二烷基硫酸钠乙醇溶液中，于80～90℃条件下搅拌30～60min，抽滤，烘干，得改性碳纳米管；(b) adding the swollen carbon nanotubes to a sodium dodecyl sulfate ethanol solution having a mass fraction of 1 to 2%, stirring at 80 to 90 ° C for 30 to 60 minutes, suction filtration, and drying to obtain a modified carbon nanoparticle. tube;
    (c)将改性碳纳米管边搅拌边加入30～40％的过氧化氢溶液中，于60～80℃恒温加热8～10h，抽滤，将过滤物用去离子水洗至pH呈中性后转移至3～4mol/L的盐酸溶液中，超声振荡4～8h，抽滤，将过滤物用去离子水洗至pH呈中性，真空烘干，即得经表面处理的碳纳米管。(c) adding the modified carbon nanotubes to a 30-40% hydrogen peroxide solution while stirring, heating at 60-80 ° C for 8-10 h, suction filtration, washing the filtrate with deionized water until the pH is neutral. After that, the solution was transferred to a 3 to 4 mol/L hydrochloric acid solution, ultrasonically shaken for 4 to 8 hours, and suction filtered, and the filtrate was washed with deionized water until the pH was neutral, and vacuum-dried to obtain surface-treated carbon nanotubes.
  5. 根据权利要求4所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，步骤(c)中，超声振荡的工艺条件为：功率4～6W，振荡时间1～2h。The method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 4, wherein in the step (c), the ultrasonic oscillation process conditions are: power 4 to 6 W, and oscillation time 1 to 2 h. .
  6. 根据权利要求1所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，步骤(1)中，所述表面活性剂为亚麻酸、十六烷基三甲基溴化铵、硬脂酸、十二烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种。 The method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 1, wherein in the step (1), the surfactant is linolenic acid or cetyltrimethyl bromide. One or more of ammonium, stearic acid, sodium lauryl sulfate, and sodium dodecylbenzenesulfonate.
  7. 根据权利要求1所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，步骤(2)中，超声分散的工艺条件为：频率15～20KHz，功率200～300W，超声时间20～30min。The method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 1, wherein in the step (2), the process condition of the ultrasonic dispersion is: a frequency of 15 to 20 KHz, and a power of 200 to 300 W, The ultrasonic time is 20 to 30 minutes.
  8. 根据权利要求7所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，超声分散期间每隔1～3min向料液中通入氢气，每次氢气通入时间5～10S，通入量为0.3～0.5m3/h。The method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 7, wherein hydrogen is introduced into the liquid solution every 1 to 3 minutes during ultrasonic dispersion, and each hydrogen gas introduction time is 5 ~10S, the amount of access is 0.3 to 0.5 m 3 /h.
  9. 根据权利要求1所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，步骤(2)中，第一次高速分散与第二次高速分散的工艺参数为：转速为6000～10000r/min，分散时间为30～60min。The method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 1, wherein in the step (2), the first high-speed dispersion and the second high-speed dispersion process parameters are: a rotation speed It is 6000~10000r/min, and the dispersion time is 30-60min.
  10. 根据权利要求1所述的一种锂离子电容器电极浆料中复合导电剂的分散方法，其特征在于，步骤(2)中，第一次高速分散与第二次高速分散均在真空条件下进行。 The method for dispersing a composite conductive agent in a lithium ion capacitor electrode slurry according to claim 1, wherein in the step (2), the first high-speed dispersion and the second high-speed dispersion are performed under vacuum conditions. .
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111430686A (en) * 2020-02-27 2020-07-17 蜂巢能源科技有限公司 Negative electrode material, battery, and vehicle
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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104658757B (en) * 2014-12-17 2017-09-29 宁波中车新能源科技有限公司 The process for dispersing of combined conductive agent in a kind of lithium-ion capacitor electrode slurry
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1770515A (en) * 2005-08-22 2006-05-10 中国科学院成都有机化学有限公司 Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof
CN103730265A (en) * 2013-12-31 2014-04-16 中国船舶重工集团公司第七一八研究所 Supercapacitor sizing manufacturing method
CN103886932A (en) * 2014-03-25 2014-06-25 深圳市纳米港有限公司 Carbon nano tube electric conduction slurry and preparation method and application thereof
CN104658757A (en) * 2014-12-17 2015-05-27 宁波南车新能源科技有限公司 Method for dispersing complex conducting agent in electrode slurry for lithium ion capacitor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102136576B (en) * 2011-01-28 2013-05-01 中航锂电（洛阳）有限公司 Conductive agent used for lithium iron phosphate battery and preparation method thereof
CN102496476A (en) 2011-11-16 2012-06-13 山东精工电子科技有限公司 Super capacitor slurry and preparation method thereof
CN102683034B (en) * 2012-04-28 2015-03-25 中国科学院电工研究所 Method for preparing super capacitor electrode plate
CN103745833A (en) * 2013-12-25 2014-04-23 东莞市迈科新能源有限公司 Super capacitor battery and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1770515A (en) * 2005-08-22 2006-05-10 中国科学院成都有机化学有限公司 Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof
CN103730265A (en) * 2013-12-31 2014-04-16 中国船舶重工集团公司第七一八研究所 Supercapacitor sizing manufacturing method
CN103886932A (en) * 2014-03-25 2014-06-25 深圳市纳米港有限公司 Carbon nano tube electric conduction slurry and preparation method and application thereof
CN104658757A (en) * 2014-12-17 2015-05-27 宁波南车新能源科技有限公司 Method for dispersing complex conducting agent in electrode slurry for lithium ion capacitor

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN113471438A (en) * 2021-06-29 2021-10-01 惠州市赛能电池有限公司 Ternary composite conductive adhesive, preparation method thereof, slurry and lithium battery
CN113471438B (en) * 2021-06-29 2022-04-22 惠州市赛能电池有限公司 Ternary composite conductive adhesive, preparation method thereof, slurry and lithium battery
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CN114725309B (en) * 2022-02-25 2023-12-12 深圳市翔丰华科技股份有限公司 Preparation method of high-performance composite conductive paste for lithium battery

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