WO2016090958A1 - Preparation method for mixed capacitor negative electrode slurry - Google Patents

Preparation method for mixed capacitor negative electrode slurry Download PDF

Info

Publication number
WO2016090958A1
WO2016090958A1 PCT/CN2015/087660 CN2015087660W WO2016090958A1 WO 2016090958 A1 WO2016090958 A1 WO 2016090958A1 CN 2015087660 W CN2015087660 W CN 2015087660W WO 2016090958 A1 WO2016090958 A1 WO 2016090958A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium titanate
carbon
slurry
preparing
mass
Prior art date
Application number
PCT/CN2015/087660
Other languages
French (fr)
Chinese (zh)
Inventor
阮殿波
杨斌
傅冠生
Original Assignee
宁波南车新能源科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宁波南车新能源科技有限公司 filed Critical 宁波南车新能源科技有限公司
Publication of WO2016090958A1 publication Critical patent/WO2016090958A1/en

Links

Classifications

    • 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
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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 preparing a hybrid capacitor negative electrode slurry.
  • Supercapacitors also known as electrochemical capacitors, have been widely used in portable digital devices due to their high current charge and discharge performance, long cycle life and high energy density.
  • it has shown good application prospects in the field of energy storage equipment such as port machinery energy feedback, rail transit, and military equipment.
  • supercapacitor electrode materials mainly use activated carbon as the electrode energy storage material, but subject to the limitation of energy density, more and more eyes are directed to the negative electrode material of lithium ion battery with stable performance and fast charge and discharge speed.
  • spinel lithium titanate with "zero strain” structure and excellent cycle stability is the most prominent, and it has become a research hotspot of a new generation of supercapacitor anode materials.
  • Spinel-type lithium titanate has its own poor conductivity, so it needs to be made into sub-micron or even nano-scale materials in the production process.
  • the change in the particle size of the material can cause the ionic resistance value of Li + in the charge storage process to decrease, the high current charge and discharge performance of the product is improved, but the electrode material and the conductive agent are bonded due to the significant increase in the agglomeration phenomenon between the particles.
  • the mixing uniformity of the agent and the like is deteriorated, and the affinity between the electrode material and the current collector is lowered, which ultimately causes difficulty in coating the material in the actual production process, and reduces the electrochemical performance and production efficiency of the supercapacitor.
  • the invention is to solve the problem of poor mixing uniformity and coating performance of the capacitor lithium titanate negative electrode slurry of the prior art, and provides a preparation method of a mixed capacitor negative electrode slurry which is simple in steps and operability and suitable for industrial production.
  • the method has the advantages that the components in the negative electrode slurry of the capacitor obtained by the method are uniform and the coating performance is good.
  • a method for preparing a hybrid capacitor anode slurry comprising the steps of:
  • the mixed slurry is subjected to high-speed dispersion for 20 to 35 minutes to obtain a mixed capacitor negative electrode slurry.
  • the high-speed dispersion time is very important. The long dispersion time will increase the viscosity of the slurry, but the dispersion will be worse.
  • the high-speed stirring will not only increase the efficiency, but also fully disperse the components and improve the uniformity and stability of the slurry. Sex.
  • the conductive agent is one or more of conductive carbon black, carbon nanotubes, and graphene.
  • the conductive agent is a mixture of conductive carbon black and graphene, or a mixture of conductive carbon black, carbon nanotubes and graphene.
  • the mass ratio of the conductive carbon black to the graphene is (3 to 5): (1 to 3), and the mass ratio of the conductive carbon black, the carbon nanotube to the graphene is (2 to 4): (1 to 3) :(1 ⁇ 3).
  • the dispersing agent is sodium carboxymethylcellulose.
  • the conductive agent generally has hydrophobicity, is not easily dispersed in water and is prone to agglomeration.
  • sodium carboxymethyl cellulose is used as a dispersing agent, and in the high-speed dispersion process, the carboxyl group on the sodium carboxymethyl cellulose causes the conductive agent.
  • the surface of the particle is negatively charged and forms an electric double layer on the surface of the conductive agent particle.
  • sodium carboxymethyl cellulose can also improve the stability of the slurry, and the slurry is less likely to settle.
  • the binder is an SBR emulsion.
  • the process parameters of stirring in the vacuum condition in the step (3) are: a vacuum degree of 0.09 to 0.1 MPa, and a stirring rate of 100 to 250 r/min.
  • the rotation speed at the time of high-speed dispersion in the step (7) is from 3,000 to 8,000 r/min.
  • the lithium titanate is carbon nanofiber-modified lithium titanate
  • the lithium titanate particles are evenly distributed on the surface and inside of the carbon nanofiber
  • the lithium titanate particles supported on the carbon nanofiber account for carbon nanometer.
  • the total mass of the fiber-modified lithium titanate is 15 to 18%.
  • the carbon nanofiber-modified lithium titanate is added to the negative electrode slurry to improve the conductivity of the negative electrode of the capacitor. After electrochemical testing, it shows excellent capacity and rate performance. And good cycle stability.
  • the carbon nanofiber-modified lithium titanate is prepared as follows: (1) the carbon nanofibers are sufficiently dispersed in isopropyl alcohol to prepare a slurry of carbon nanofibers;
  • Lithium carbonate and titanium dioxide are respectively weighed according to a molar ratio of lithium element to titanium element of 3.5 to 4.5:5, and added to the slurry obtained in the step (1), and thoroughly mixed to obtain a precursor slurry. ;
  • the precursor slurry obtained in the step (2) is spray-dried and granulated to obtain a precursor powder
  • the precursor powder obtained in the step (3) is calcined at 800 to 900 ° C for 1 to 10 hours, and after cooling, the carbon nanofiber-modified lithium titanate is obtained.
  • the conductive agent is a modified carbon nanotube, and the steps of preparing the modified carbon nanotube are as follows:
  • the secondary modified carbon nanotubes and the perchloric acid having a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 60-70 ° C for 24 hours, cooled, filtered, washed with water, The modified carbon nanotubes are obtained after vacuum drying.
  • Typical multi-walled carbon nanotubes generally have a diameter of a few nanometers to several tens of nanometers and a length of several to several tens of micrometers.
  • the prepared samples are mostly disorderly distributed, and the carbon nanotubes are intertwined and difficult to disperse, and the agglomerated carbon nanotubes need to be dispersed into individual carbon nanotubes to exert their special properties.
  • the step (1) mixes the carbon nanotubes with a dimethylformamide solution and an acid solution having a mass concentration of 30-50%, and simultaneously stirs to expand the carbon nanotubes and the liquid.
  • the contact surface enables the carbon nanotubes to be uniformly dispersed, and the specific solvent combination system of the dimethylformamide solution and the acid solution having a mass concentration of 30-50% can make the carbon nanotubes disperse more uniformly in the system and effectively avoid the carbon nanotubes. Reunion.
  • Step (1) firstly dispersing the carbon nanotubes uniformly, which facilitates the shearing of the step (2), and hydrothermally reacts the uniformly dispersed carbon nanotubes of the step (1) with the specific chemical shear liquid of the present invention, thereby effectively cutting the carbon.
  • Nano The tube is obtained by homogenizing carbon nanotubes having a relatively uniform length (about 100-150 nm in length), and such carbon nanotubes can exert more excellent electrical and thermal conduction effects in a smaller amount when used for an electrode material.
  • Step (3) The homogenized carbon nanotube obtained in the step (2) is hydrothermally reacted in perchloric acid, and the perchloric acid molecule can intercalate and swell the carbon nanotube bundle, so that the carbon nanotubes are separated from each other and the surface thereof is highly reacted.
  • the activated carbonaceous by-products are exposed to achieve selective functionalization of carbonaceous by-products. Similar to surfactants, these functionalized carbon by-products have amphiphilic properties, which can improve the interaction between carbon nanotubes and binders, assist in the dispersion of carbon nanotubes, and greatly improve the preparation of positive and negative materials for carbon nanotubes. Uniform dispersion performance.
  • the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1-2:1.
  • the chemical shearing solution is a mixture of a sodium molybdate solution having a concentration of 0.5 to 0.8 mol/L and a silicomolybdic acid solution having a concentration of 0.3 to 0.5 mol/L in a volume ratio of 1:1.
  • the present invention has the following beneficial effects:
  • the hybrid capacitor product using the hybrid capacitor negative electrode slurry described above exhibits excellent capacity and rate performance as well as good cycle stability performance.
  • the mixed slurry was subjected to high-speed dispersion at a rotational speed of 3000 r/min for 20 minutes to obtain a mixed capacitor negative electrode slurry.
  • This embodiment is different from the embodiment 1 in that the conductive agent is a mixture of conductive carbon black and graphene in a mass ratio of 2:1, and the others are completely the same.
  • This embodiment is different from the embodiment 1 in that the conductive agent is a mixture of conductive carbon black and graphene in a mass ratio of 5:3, and the others are completely the same.
  • each raw material according to the following mass percentage: 10% conductive agent, 5% dispersing agent, 5% binder, 80% lithium titanate; and weigh the mass of conductive agent, dispersant, binder and titanium
  • the deionized water has a total mass of 60% of lithium acid, wherein the conductive agent is a mixture of conductive carbon black, carbon nanotubes and graphene in a mass ratio of 2:1:1, and the dispersing agent is sodium carboxymethylcellulose.
  • the binder is an SBR emulsion;
  • the mixed slurry was subjected to high-speed dispersion at a rotational speed of 8000 r/min for 35 minutes to obtain a mixed capacitor negative electrode slurry.
  • This embodiment differs from the embodiment 4 in that the conductive agent is a mixture of conductive carbon black, carbon nanotubes and graphene in a mass ratio of 3:2:2, and the others are identical.
  • This embodiment differs from the embodiment 4 in that the conductive agent is a mixture of conductive carbon black, carbon nanotubes and graphene in a mass ratio of 4:3:3, and the others are identical.
  • the mixed slurry was subjected to high-speed dispersion at a rotational speed of 6000 r/min for 30 minutes to obtain a mixed capacitor negative electrode slurry.
  • Embodiment 7 This embodiment is different from Embodiment 7 in that the conductive agent is carbon nanotubes, and the others are identical.
  • Embodiment 7 This embodiment is different from Embodiment 7 in that the conductive agent is graphene, and the others are identical.
  • the lithium titanate is a carbon nanofiber-modified lithium titanate, and the lithium titanate particles are evenly distributed on the surface and inside of the carbon nanofiber, and the carbon nanofiber is loaded on the carbon nanofiber.
  • the lithium titanate particles account for 18% of the total mass of the carbon nanofiber-modified lithium titanate.
  • the negative electrode material is made of the electrochemical capacity at 1C reached 171mAh g -1, the capacity can be at 100C to 125mAh g -1.
  • the lithium titanate is a carbon nanofiber-modified lithium titanate, and the lithium titanate particles are evenly distributed on the surface and inside of the carbon nanofiber, and the carbon nanofiber is loaded on the carbon nanofiber.
  • the lithium titanate particles account for 15% of the total mass of the carbon nanofiber-modified lithium titanate; the preparation method of the carbon nanofiber-modified lithium titanate is as follows:
  • the carbon nanofibers are sufficiently dispersed in isopropyl alcohol to prepare a carbon nanofiber slurry having a solid content of 1%;
  • lithium carbonate and titanium dioxide are respectively weighed and added to the slurry prepared in the step (1), so that lithium titanate is modified in the carbon nanofiber.
  • the mass percentage of lithium titanate is stirred at 85% and 200 rpm for 30 minutes to be thoroughly mixed to obtain a precursor slurry;
  • the precursor slurry obtained in the step (2) is spray-dried, and granulated at 280 ° C to obtain a precursor powder;
  • the precursor powder obtained in the step (3) was baked at 900 ° C for 6 hours, and after cooling, the carbon nanofiber-modified lithium titanate was obtained.
  • the negative electrode material is made of the electrochemical capacity at 1C reached 172mAh g -1, the capacity can be at 100C to 130mAh g -1.
  • the conductive agent is a modified carbon nanotube
  • the steps of preparing the modified carbon nanotube are as follows:
  • the chemical shear solution is a mixture of a sodium molybdate solution having a concentration of 0.65 mol/L and a silicomolybdic acid solution having a concentration of 0.4 mol/L in a volume ratio of 1:1;
  • the negative electrode slurry of the first to the second embodiments of the present invention is coated, rolled, punched, laminated, injected, and formed into a lithium titanate hybrid capacitor of the same specification.
  • the performance parameters such as resistance, cycle life and energy density were measured.
  • the experimental results are shown in Table 1.
  • the obtained lithium titanate negative electrode slurry capacitor prepared by the method of the invention has high energy density and outstanding electrochemical performance, indicating that the slurry obtained by the invention has good uniformity and stability, and It is beneficial to improve the electrochemical performance of the capacitor.

Abstract

Disclosed is a preparation method for a mixed capacitor negative electrode slurry. The preparation method comprises the following steps: (1) weighing the following components in mass percent: 5 to 10 percent of a conductive agent, 3 to 5 percent of a dispersing agent, 3 to 5 percent of a binding agent and 80 to 89 percent of lithium titanate; meanwhile, weighing deionized water of which the mass is 40 to 60 percent of the total mass of the conductive agent, the dispersing agent, the binding agent and the lithium titanate; (2) adding the dispersing agent to the deionized water accounting for 40 to 60 percent of total water, and evenly stirring, and then standing for 12-24 h to obtain a dispersion mother solution; (3) adding the conductive agent to the dispersion mother solution, and then stirring for 0.5-1 h under the vacuum condition; adding the lithium titanate when the material is cooled to a room temperature, and stirring for 0.5-1 h under the same condition; adding the binding agent and the remaining deionized water after the material is cooled to the room temperature, and stirring for 0.5-1 h under the same condition, and then, cooling the material to the room temperature to obtain a mixed slurry; and (4) performing high-speed dispersion on the mixed slurry for 20-35 min to obtain the mixed capacitor negative electrode slurry. The present invention is highly operable and is suitable for industrial production; the prepared capacitor negative electrode slurry has high homogeneity and coating performance.

Description

一种混合型电容器负极浆料制备方法Method for preparing mixed capacitor anode slurry 技术领域Technical field
本发明涉及超级电容器技术领域，尤其是涉及一种混合型电容器负极浆料制备方法。The present invention relates to the field of supercapacitor technology, and in particular, to a method for preparing a hybrid capacitor negative electrode slurry.
背景技术Background technique
超级电容器又称为电化学电容器，因其具有大电流充放电性能、超长的循环使用寿命以及较高的能量密度，在众多的储能器件中受到广泛的关注，现已广泛应用于便携式数码设备产品、移动通讯、混合动力大巴和风电变桨***等产品中。近年来在港机能量回馈、轨道交通、军工装备等储能装备领域显示出了良好的应用前景。Supercapacitors, also known as electrochemical capacitors, have been widely used in portable digital devices due to their high current charge and discharge performance, long cycle life and high energy density. Equipment products, mobile communications, hybrid buses and wind power pitch systems. In recent years, it has shown good application prospects in the field of energy storage equipment such as port machinery energy feedback, rail transit, and military equipment.
目前，超级电容器电极材料主要采用活性炭作为电极储能材料，但是受制于能量密度的限制使得越来越多的目光投向性能稳定、充放电速度快的锂离子电池负极材料。这其中以具有“零应变”结构、优异循环稳定性的尖晶石型钛酸锂最为突出，成为了新一代超级电容器负极材料的研究热点。尖晶石型钛酸锂才有由于本身导电性较差，因此生产过程中需要将其制成亚微米甚至纳米级材料。此时，尽管材料粒度的变化能够使得Li+在电荷存储过程中的离子电阻值下降，产品的大电流充放电性能提高，但由于颗粒间团聚现象的明显增加、电极材料与导电剂、粘结剂等的混合均一性变差、电极材料与集流体的亲和性降低，最终造成材料在实际生产过程中涂覆困难，降低了超级电容器的电化学性能与生产效率。At present, supercapacitor electrode materials mainly use activated carbon as the electrode energy storage material, but subject to the limitation of energy density, more and more eyes are directed to the negative electrode material of lithium ion battery with stable performance and fast charge and discharge speed. Among them, spinel lithium titanate with "zero strain" structure and excellent cycle stability is the most prominent, and it has become a research hotspot of a new generation of supercapacitor anode materials. Spinel-type lithium titanate has its own poor conductivity, so it needs to be made into sub-micron or even nano-scale materials in the production process. At this time, although the change in the particle size of the material can cause the ionic resistance value of Li + in the charge storage process to decrease, the high current charge and discharge performance of the product is improved, but the electrode material and the conductive agent are bonded due to the significant increase in the agglomeration phenomenon between the particles. The mixing uniformity of the agent and the like is deteriorated, and the affinity between the electrode material and the current collector is lowered, which ultimately causes difficulty in coating the material in the actual production process, and reduces the electrochemical performance and production efficiency of the supercapacitor.
发明内容Summary of the invention
本发明是为了解决现有技术的电容器钛酸锂负极浆料混合均匀性与涂覆性能差的问题，提供了一种步骤简单，可操作性强，适合工业化生产的混合型电容器负极浆料制备方法，通过该方法制得的电容器负极浆料中组分均一稳定，涂覆性能好。The invention is to solve the problem of poor mixing uniformity and coating performance of the capacitor lithium titanate negative electrode slurry of the prior art, and provides a preparation method of a mixed capacitor negative electrode slurry which is simple in steps and operability and suitable for industrial production. The method has the advantages that the components in the negative electrode slurry of the capacitor obtained by the method are uniform and the coating performance is good.
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:
一种混合型电容器负极浆料制备方法，其特征在于，包括以下步骤：A method for preparing a hybrid capacitor anode slurry, comprising the steps of:
(1)按以下质量百分比称取各原料：5～10％导电剂，3～5％分散剂，3～5％粘结剂，80～89％钛酸锂，上述各组分质量百分比之和为100％；同时称取质量为 导电剂、分散剂、粘结剂和钛酸锂总质量40～60％的去离子水。本发明对浆料的配方进行优化改进，整个配方环保无污染，且粘度适中，涂覆性能好。(1) Weigh each raw material by the following mass percentage: 5-10% conductive agent, 3~5% dispersant, 3~5% binder, 80-89% lithium titanate, the sum of the mass percentages of the above components 100%; at the same time weigh the quality The conductive agent, dispersant, binder and lithium titanate have a total mass of 40 to 60% deionized water. The invention optimizes and improves the formulation of the slurry, and the whole formula is environmentally friendly and non-polluting, and has moderate viscosity and good coating performance.
(2)向占总水量40～60％的去离子水中加入分散剂，搅拌均匀后静置12～24h，得分散母液。(2) Adding a dispersing agent to deionized water containing 40 to 60% of the total water amount, stirring uniformly, and then standing for 12 to 24 hours to obtain a dispersion mother liquid.
(3)在分散母液中加入导电剂后在真空条件下搅拌0.5～1h，待物料冷却至室温时加入钛酸锂并以相同条件搅拌0.5～1h，待物料冷却至室温时加入粘结剂和剩余的去离子水，以相同条件搅拌0.5～1h后将物料冷却至室温，得混合浆料。(3) adding conductive agent to the dispersion mother liquid and stirring under vacuum for 0.5 to 1 h. When the material is cooled to room temperature, lithium titanate is added and stirred under the same conditions for 0.5 to 1 h, and the binder is added after the material is cooled to room temperature. The remaining deionized water was stirred under the same conditions for 0.5 to 1 hour, and then the material was cooled to room temperature to obtain a mixed slurry.
(4)对混合浆料进行高速分散20～35min即得混合型电容器负极浆料。高速分散时间十分关键，分散时间长，会使浆料的粘度增大，反而分散性会变差，通过高速搅拌不仅效率高，而且能使各组分充分分散，提高浆料的均一性与稳定性。(4) The mixed slurry is subjected to high-speed dispersion for 20 to 35 minutes to obtain a mixed capacitor negative electrode slurry. The high-speed dispersion time is very important. The long dispersion time will increase the viscosity of the slurry, but the dispersion will be worse. The high-speed stirring will not only increase the efficiency, but also fully disperse the components and improve the uniformity and stability of the slurry. Sex.
作为优选，所述导电剂为导电炭黑、碳纳米管、石墨烯中的一种或多种。Preferably, the conductive agent is one or more of conductive carbon black, carbon nanotubes, and graphene.
作为优选，所述导电剂为导电炭黑和石墨烯的混合物，或导电碳黑、碳纳米管与石墨烯的混合物。Preferably, the conductive agent is a mixture of conductive carbon black and graphene, or a mixture of conductive carbon black, carbon nanotubes and graphene.
作为优选，导电碳黑与石墨烯的质量比为(3～5):(1～3)，导电碳黑、碳纳米管与石墨烯的质量比为(2～4)：(1～3)：(1～3)。Preferably, the mass ratio of the conductive carbon black to the graphene is (3 to 5): (1 to 3), and the mass ratio of the conductive carbon black, the carbon nanotube to the graphene is (2 to 4): (1 to 3) :(1~3).
作为优选，所述分散剂为羧甲基纤维素钠。导电剂一般均具有憎水性，在水中不易分散且易发生团聚现象，本发明中采用羧甲基纤维素钠作为分散剂，在高速分散过程中，羧甲基纤维素钠上羧基会使导电剂颗粒表面带上负电荷，并在导电剂颗粒表面形成双电层，当2个被包裹的导电剂颗粒相接近时，同性电荷产生相互排斥，迫使2个被包裹的导电剂颗粒分离，从而提高导电剂的分散性，另外羧甲基纤维素钠还能提高浆料的稳定性，浆料不易发生沉降。Preferably, the dispersing agent is sodium carboxymethylcellulose. The conductive agent generally has hydrophobicity, is not easily dispersed in water and is prone to agglomeration. In the present invention, sodium carboxymethyl cellulose is used as a dispersing agent, and in the high-speed dispersion process, the carboxyl group on the sodium carboxymethyl cellulose causes the conductive agent. The surface of the particle is negatively charged and forms an electric double layer on the surface of the conductive agent particle. When the two encapsulated conductive agent particles are close to each other, the same charge is mutually repelled, forcing the two encapsulated conductive agent particles to separate, thereby improving The dispersibility of the conductive agent, in addition, sodium carboxymethyl cellulose can also improve the stability of the slurry, and the slurry is less likely to settle.
作为优选，所述粘结剂为SBR乳液。Preferably, the binder is an SBR emulsion.
作为优选，步骤(3)中真空条件下搅拌的工艺参数为：真空度为0.09～0.1MPa，搅拌速率为100～250r/min。Preferably, the process parameters of stirring in the vacuum condition in the step (3) are: a vacuum degree of 0.09 to 0.1 MPa, and a stirring rate of 100 to 250 r/min.
作为优选，步骤(7)中高速分散时的转速为3000～8000r/min。Preferably, the rotation speed at the time of high-speed dispersion in the step (7) is from 3,000 to 8,000 r/min.
作为优选，所述钛酸锂为碳纳米纤维改性钛酸锂，所述钛酸锂颗粒均匀分布于所述碳纳米纤维的表面和内部，碳纳米纤维上负载的钛酸锂颗粒占碳纳米纤维改性钛酸锂总质量的15～18％。碳纳米纤维改性钛酸锂加入负极浆料中，可以提高电容器负极的导电性能。经过电化学测试，显示出优异的容量和倍率性能以 及良好的循环稳定性能。Preferably, the lithium titanate is carbon nanofiber-modified lithium titanate, the lithium titanate particles are evenly distributed on the surface and inside of the carbon nanofiber, and the lithium titanate particles supported on the carbon nanofiber account for carbon nanometer. The total mass of the fiber-modified lithium titanate is 15 to 18%. The carbon nanofiber-modified lithium titanate is added to the negative electrode slurry to improve the conductivity of the negative electrode of the capacitor. After electrochemical testing, it shows excellent capacity and rate performance. And good cycle stability.
作为优选，所述碳纳米纤维改性钛酸锂的制备方法如下：(1)将碳纳米纤维在异丙醇中充分分散，制备出碳纳米纤维的浆料；Preferably, the carbon nanofiber-modified lithium titanate is prepared as follows: (1) the carbon nanofibers are sufficiently dispersed in isopropyl alcohol to prepare a slurry of carbon nanofibers;
(2)按照锂元素与钛元素摩尔比为3.5～4.5:5的比例分别称取碳酸锂与二氧化钛，将其加入到步骤(1)制得的浆料中，充分混合，得到前驱体浆料；(2) Lithium carbonate and titanium dioxide are respectively weighed according to a molar ratio of lithium element to titanium element of 3.5 to 4.5:5, and added to the slurry obtained in the step (1), and thoroughly mixed to obtain a precursor slurry. ;
(3)将步骤(2)得到的前驱体浆料进行喷雾干燥造粒，得到前驱体粉体；(3) the precursor slurry obtained in the step (2) is spray-dried and granulated to obtain a precursor powder;
(4)将步骤(3)得到的前驱体粉体于800～900℃焙烧1～10小时，冷却后即得到所述碳纳米纤维改性钛酸锂。(4) The precursor powder obtained in the step (3) is calcined at 800 to 900 ° C for 1 to 10 hours, and after cooling, the carbon nanofiber-modified lithium titanate is obtained.
作为优选，所述导电剂为改性碳纳米管，改性碳纳米管的制备方法步骤如下：Preferably, the conductive agent is a modified carbon nanotube, and the steps of preparing the modified carbon nanotube are as follows:
(1)将碳纳米管、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：10-20mL：5-15mL的料液比混合，控制温度35-45℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，80-100℃下真空干燥30-60min得初级改性碳纳米管；(1) mixing carbon nanotubes, a concentration of 30-50% dimethylformamide solution and an acid solution according to a ratio of material to liquid of 1g: 10-20mL: 5-15mL, and mixing and controlling at a temperature of 35-45 ° C. -50min, filtration, washing with water and anhydrous ethanol, vacuum drying at 80-100 ° C for 30-60min to obtain primary modified carbon nanotubes;
(2)将初级改性碳纳米管与化学剪切液按照1g：30-50mL的料液比混合，加热至150-180℃，水热反应40-60h，冷却，水洗，得次级改性碳纳米管；(2) mixing the primary modified carbon nanotubes with the chemical shear liquid according to the ratio of material to liquid of 1g: 30-50mL, heating to 150-180 ° C, hydrothermal reaction for 40-60 hours, cooling, washing with water to obtain secondary modification. Carbon nanotubes;
(3)次级改性碳纳米管与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至60-70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管。(3) The secondary modified carbon nanotubes and the perchloric acid having a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 60-70 ° C for 24 hours, cooled, filtered, washed with water, The modified carbon nanotubes are obtained after vacuum drying.
研究表明：在包含碳纳米管的电极中，当碳纳米管的数量大到足以使碳纳米管能够彼此接触时，才能使电极不受碳纳米管自身的电阻影响，而主要受相互之间的接触电阻影响。因此在添加碳纳米管时需要的量就会较大。典型的多壁碳纳米管的直径一般为几纳米至几十纳米，长度为几至几十微米。制备的样品多呈杂乱分布，碳纳米管之间相互缠绕难以分散，成团状的碳纳米管需要被分散成单个的碳纳米管，才能发挥其特殊性能。Studies have shown that in the electrode containing carbon nanotubes, when the number of carbon nanotubes is large enough to enable the carbon nanotubes to contact each other, the electrodes are not affected by the resistance of the carbon nanotubes themselves, but mainly by each other. Contact resistance effect. Therefore, the amount required for the addition of carbon nanotubes is large. Typical multi-walled carbon nanotubes generally have a diameter of a few nanometers to several tens of nanometers and a length of several to several tens of micrometers. The prepared samples are mostly disorderly distributed, and the carbon nanotubes are intertwined and difficult to disperse, and the agglomerated carbon nanotubes need to be dispersed into individual carbon nanotubes to exert their special properties.
改性碳纳米管的制备方法中，步骤(1)将碳纳米管与质量浓度30-50％的二甲基甲酰胺溶液及酸溶液混合，同时辅以搅拌，以扩大碳纳米管与液体的接触面，使得碳纳米管分散均匀，质量浓度30-50％的二甲基甲酰胺溶液及酸溶液的特定溶剂组合体系，能够使得碳纳米管能在体系中分散更均匀，有效避免碳纳米管团聚。步骤(1)先将碳纳米管分散均匀，这样利于步骤(2)的剪切，将步骤(1)分散均匀的碳纳米管与本发明特定的化学剪切液水热反应，能有效切断碳纳米 管，获得长度较均一(长度大约在100-150nm)左右的均一化碳纳米管，这样的碳纳米管在用于电极材料时，可以用更少的量发挥更优异的导电导热效果。步骤(3)将步骤(2)得到的均一化碳纳米管在高氯酸中水热反应，高氯酸分子能够插层、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碳质副产物暴露出来，从而实现选择性功能化碳质副产物。与表面活性剂类似，这些功能化的碳质副产物具有两亲性，可改善碳纳米管与粘结剂的相互作用，协助碳纳米管分散，从而大大提高碳纳米管在制备正负极材料时的均匀分散性能。In the preparation method of the modified carbon nanotubes, the step (1) mixes the carbon nanotubes with a dimethylformamide solution and an acid solution having a mass concentration of 30-50%, and simultaneously stirs to expand the carbon nanotubes and the liquid. The contact surface enables the carbon nanotubes to be uniformly dispersed, and the specific solvent combination system of the dimethylformamide solution and the acid solution having a mass concentration of 30-50% can make the carbon nanotubes disperse more uniformly in the system and effectively avoid the carbon nanotubes. Reunion. Step (1) firstly dispersing the carbon nanotubes uniformly, which facilitates the shearing of the step (2), and hydrothermally reacts the uniformly dispersed carbon nanotubes of the step (1) with the specific chemical shear liquid of the present invention, thereby effectively cutting the carbon. Nano The tube is obtained by homogenizing carbon nanotubes having a relatively uniform length (about 100-150 nm in length), and such carbon nanotubes can exert more excellent electrical and thermal conduction effects in a smaller amount when used for an electrode material. Step (3) The homogenized carbon nanotube obtained in the step (2) is hydrothermally reacted in perchloric acid, and the perchloric acid molecule can intercalate and swell the carbon nanotube bundle, so that the carbon nanotubes are separated from each other and the surface thereof is highly reacted. The activated carbonaceous by-products are exposed to achieve selective functionalization of carbonaceous by-products. Similar to surfactants, these functionalized carbon by-products have amphiphilic properties, which can improve the interaction between carbon nanotubes and binders, assist in the dispersion of carbon nanotubes, and greatly improve the preparation of positive and negative materials for carbon nanotubes. Uniform dispersion performance.
作为优选，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1-2:1的体积比的混合物。Preferably, the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1-2:1.
作为优选，所述化学剪切液为浓度0.5-0.8moL/L的钼酸钠溶液与浓度0.3-0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。Preferably, the chemical shearing solution is a mixture of a sodium molybdate solution having a concentration of 0.5 to 0.8 mol/L and a silicomolybdic acid solution having a concentration of 0.3 to 0.5 mol/L in a volume ratio of 1:1.
一种采用所述的混合型电容器负极浆料的混合型电容器。A hybrid capacitor using the hybrid capacitor negative electrode slurry described above.
因此，本发明具有如下有益效果：Therefore, the present invention has the following beneficial effects:
(1)对浆料的配方进行优化改进，整个配方环保无污染，且粘度适中，涂覆性能好；(1) Optimize and improve the formulation of the slurry, the whole formula is environmentally friendly and non-polluting, and the viscosity is moderate, and the coating performance is good;
(2)通过分步添加各组分以及高速分散保证浆料的均匀性，并通过添加分散剂羧甲基纤维素钠有效解决了导电剂颗粒不易分散的问题；(2) ensuring the uniformity of the slurry by stepwise addition of each component and high-speed dispersion, and effectively solving the problem that the conductive agent particles are not easily dispersed by adding the dispersing agent sodium carboxymethylcellulose;
(3)步骤简单，可操作性强，适合工业化生产；(3) The steps are simple, the operability is strong, and it is suitable for industrial production;
(4)采用所述的混合型电容器负极浆料的混合型电容器产品显示出优异的容量和倍率性能以及良好的循环稳定性能。(4) The hybrid capacitor product using the hybrid capacitor negative electrode slurry described above exhibits excellent capacity and rate performance as well as good cycle stability performance.
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)按以下质量百分比称取各原料：5％导电剂，3％分散剂，3％粘结剂，89％钛酸锂；同时称取质量为导电剂、分散剂、粘结剂和钛酸锂总质量40％的去离子水，其中，导电剂为导电炭黑与石墨烯按质量比3：1混合而成的混合物， 分散剂为羧甲基纤维素钠，粘结剂为SBR乳液；(1) Weigh each raw material by the following mass percentage: 5% conductive agent, 3% dispersant, 3% binder, 89% lithium titanate; and weigh the mass of conductive agent, dispersant, binder and titanium The total mass of lithium acid is 40% deionized water, wherein the conductive agent is a mixture of conductive carbon black and graphene in a mass ratio of 3:1. The dispersing agent is sodium carboxymethyl cellulose, and the binder is an SBR emulsion;
(2)向占总水量40％的去离子水中加入分散剂，搅拌均匀后静置12h，得分散母液；(2) adding a dispersing agent to deionized water containing 40% of the total water amount, stirring uniformly, and then standing for 12 hours to obtain a dispersion mother liquid;
(3)在分散母液中加入导电剂后在真空条件下搅拌0.5h，待物料冷却至室温时加入钛酸锂并以相同条件搅拌0.5h，待物料冷却至室温时加入粘结剂和剩余的去离子水，以相同条件搅拌0.5h后将物料冷却至室温，得混合浆料，真空条件下搅拌的工艺参数为：真空度为0.09MPa，搅拌速率为100r/min；(3) adding conductive agent to the dispersion mother liquid and stirring under vacuum for 0.5 h. When the material is cooled to room temperature, lithium titanate is added and stirred under the same conditions for 0.5 h. When the material is cooled to room temperature, the binder and the remaining are added. Deionized water, stirred under the same conditions for 0.5 h, the material was cooled to room temperature to obtain a mixed slurry, and the process parameters under vacuum were as follows: vacuum degree was 0.09 MPa, stirring rate was 100 r/min;
(4)对混合浆料以转速3000r/min进行高速分散20min，即得混合型电容器负极浆料。(4) The mixed slurry was subjected to high-speed dispersion at a rotational speed of 3000 r/min for 20 minutes to obtain a mixed capacitor negative electrode slurry.
实施例2Example 2
本实施例与实施例1的不同之处在于：导电剂为导电炭黑与石墨烯按质量比2：1混合而成的混合物，其余完全相同。This embodiment is different from the embodiment 1 in that the conductive agent is a mixture of conductive carbon black and graphene in a mass ratio of 2:1, and the others are completely the same.
实施例3Example 3
本实施例与实施例1的不同之处在于：导电剂为导电炭黑与石墨烯按质量比5：3混合而成的混合物，其余完全相同。This embodiment is different from the embodiment 1 in that the conductive agent is a mixture of conductive carbon black and graphene in a mass ratio of 5:3, and the others are completely the same.
实施例4Example 4
(1)按以下质量百分比称取各原料：10％导电剂，5％分散剂，5％粘结剂，80％钛酸锂；同时称取质量为导电剂、分散剂、粘结剂和钛酸锂总质量60％的去离子水，其中，导电剂为导电碳黑、碳纳米管与石墨烯按质量比2：1：1混合而成的混合物，分散剂为羧甲基纤维素钠，粘结剂为SBR乳液；(1) Weigh each raw material according to the following mass percentage: 10% conductive agent, 5% dispersing agent, 5% binder, 80% lithium titanate; and weigh the mass of conductive agent, dispersant, binder and titanium The deionized water has a total mass of 60% of lithium acid, wherein the conductive agent is a mixture of conductive carbon black, carbon nanotubes and graphene in a mass ratio of 2:1:1, and the dispersing agent is sodium carboxymethylcellulose. The binder is an SBR emulsion;
(2)向占总水量60％的去离子水中加入分散剂，搅拌均匀后静置24h，得分散母液；(2) adding a dispersing agent to deionized water containing 60% of the total water amount, stirring uniformly, and then standing for 24 hours to obtain a dispersion mother liquid;
(3)在分散母液中加入导电剂后在真空条件下搅拌1h，待物料冷却至室温时加入钛酸锂并以相同条件搅拌1h，待物料冷却至室温时加入粘结剂和剩余的去离子水，以相同条件搅拌1h后将物料冷却至室温，得混合浆料，真空条件下搅拌的工艺参数为：真空度为0.1MPa，搅拌速率为250r/min； (3) Adding a conductive agent to the dispersion mother liquid and stirring under vacuum for 1 hour. When the material is cooled to room temperature, lithium titanate is added and stirred under the same conditions for 1 hour. When the material is cooled to room temperature, the binder and the remaining deionized are added. The water was stirred under the same conditions for 1 hour, and then the material was cooled to room temperature to obtain a mixed slurry. The process parameters under vacuum conditions were as follows: a vacuum of 0.1 MPa and a stirring rate of 250 r/min;
(4)对混合浆料以转速8000r/min进行高速分散35min，即得混合型电容器负极浆料。(4) The mixed slurry was subjected to high-speed dispersion at a rotational speed of 8000 r/min for 35 minutes to obtain a mixed capacitor negative electrode slurry.
实施例5Example 5
本实施例与实施例4的不同之处在于：导电剂为导电碳黑、碳纳米管与石墨烯按质量比3：2：2混合而成的混合物，其他完全相同。This embodiment differs from the embodiment 4 in that the conductive agent is a mixture of conductive carbon black, carbon nanotubes and graphene in a mass ratio of 3:2:2, and the others are identical.
实施例6Example 6
本实施例与实施例4的不同之处在于：导电剂为导电碳黑、碳纳米管与石墨烯按质量比4：3：3混合而成的混合物，其他完全相同。This embodiment differs from the embodiment 4 in that the conductive agent is a mixture of conductive carbon black, carbon nanotubes and graphene in a mass ratio of 4:3:3, and the others are identical.
实施例7Example 7
(1)按以下质量百分比称取各原料：6％导电剂，4％分散剂，4％粘结剂，86％钛酸锂；同时称取质量为导电剂、分散剂、粘结剂和钛酸锂总质量50％的去离子水，其中，导电剂为导电碳黑，分散剂为羧甲基纤维素钠，粘结剂为SBR乳液；(1) Weigh each raw material by the following mass percentage: 6% conductive agent, 4% dispersant, 4% binder, 86% lithium titanate; and weigh the mass of conductive agent, dispersant, binder and titanium Deionized water having a total mass of lithium acid of 50%, wherein the conductive agent is conductive carbon black, the dispersing agent is sodium carboxymethyl cellulose, and the binder is SBR emulsion;
(2)向占总水量50％的去离子水中加入分散剂，搅拌均匀后静置18h，得分散母液；(2) adding a dispersing agent to deionized water containing 50% of the total water amount, stirring uniformly and then standing for 18 hours to obtain a dispersion mother liquid;
(3)在分散母液中加入导电剂后在真空条件下搅拌0.8h，待物料冷却至室温时加入钛酸锂并以相同条件搅拌0.8h，待物料冷却至室温时加入粘结剂和剩余的去离子水，以相同条件搅拌0.8h后将物料冷却至室温，得混合浆料，真空条件下搅拌的工艺参数为：真空度为0.095MPa，搅拌速率为200r/min；(3) Adding a conductive agent to the dispersion mother liquid and stirring under vacuum for 0.8 h. When the material is cooled to room temperature, lithium titanate is added and stirred under the same conditions for 0.8 h. When the material is cooled to room temperature, the binder and the remaining are added. Deionized water, stirred under the same conditions for 0.8 h, and then the material was cooled to room temperature to obtain a mixed slurry. The process parameters under vacuum conditions were: vacuum degree of 0.095 MPa, stirring rate of 200 r/min;
(4)对混合浆料以转速6000r/min进行高速分散30min，即得混合型电容器负极浆料。(4) The mixed slurry was subjected to high-speed dispersion at a rotational speed of 6000 r/min for 30 minutes to obtain a mixed capacitor negative electrode slurry.
实施例8Example 8
本实施例与实施例7的不同之处在于：导电剂为碳纳米管，其他完全相同。This embodiment is different from Embodiment 7 in that the conductive agent is carbon nanotubes, and the others are identical.
实施例9Example 9
本实施例与实施例7的不同之处在于：导电剂为石墨烯，其他完全相同。 This embodiment is different from Embodiment 7 in that the conductive agent is graphene, and the others are identical.
实施例10Example 10
本实施例与实施例1的不同之处在于：钛酸锂为碳纳米纤维改性钛酸锂，所述钛酸锂颗粒均匀分布于所述碳纳米纤维的表面和内部，碳纳米纤维上负载的钛酸锂颗粒占碳纳米纤维改性钛酸锂总质量的18％。The difference between this embodiment and the embodiment 1 is that the lithium titanate is a carbon nanofiber-modified lithium titanate, and the lithium titanate particles are evenly distributed on the surface and inside of the carbon nanofiber, and the carbon nanofiber is loaded on the carbon nanofiber. The lithium titanate particles account for 18% of the total mass of the carbon nanofiber-modified lithium titanate.
经过恒电流充放电测试，结果表明该材料制成的负极在1C下的电化学容量达到171mAh g-1，在100C下容量能够到125mAh g-1。After constant current charge-discharge test results showed that the negative electrode material is made of the electrochemical capacity at 1C reached 171mAh g -1, the capacity can be at 100C to 125mAh g -1.
实施例11Example 11
本实施例与实施例10的不同之处在于：钛酸锂为碳纳米纤维改性钛酸锂，所述钛酸锂颗粒均匀分布于所述碳纳米纤维的表面和内部，碳纳米纤维上负载的钛酸锂颗粒占碳纳米纤维改性钛酸锂总质量的15％；所述碳纳米纤维改性钛酸锂的制备方法如下：The difference between this embodiment and the embodiment 10 is that the lithium titanate is a carbon nanofiber-modified lithium titanate, and the lithium titanate particles are evenly distributed on the surface and inside of the carbon nanofiber, and the carbon nanofiber is loaded on the carbon nanofiber. The lithium titanate particles account for 15% of the total mass of the carbon nanofiber-modified lithium titanate; the preparation method of the carbon nanofiber-modified lithium titanate is as follows:
(1)将碳纳米纤维在异丙醇中充分分散，制备出固含率在1％的碳纳米纤维浆料；(1) The carbon nanofibers are sufficiently dispersed in isopropyl alcohol to prepare a carbon nanofiber slurry having a solid content of 1%;
(2)按照锂元素与钛元素摩尔比为4.5:5的比例分别称取含碳酸锂与二氧化钛，将其加入到步骤(1)制得的浆料中，使得钛酸锂在碳纳米纤维改性钛酸锂的质量百分含量在85％，200rpm转速下搅拌30分钟以充分混合，得到前驱体浆料；(2) According to the ratio of the molar ratio of lithium element to titanium element of 4.5:5, lithium carbonate and titanium dioxide are respectively weighed and added to the slurry prepared in the step (1), so that lithium titanate is modified in the carbon nanofiber. The mass percentage of lithium titanate is stirred at 85% and 200 rpm for 30 minutes to be thoroughly mixed to obtain a precursor slurry;
(3)将步骤(2)得到的前驱体浆料进行喷雾干燥，在280℃下进行造粒，得到前驱体粉体；(3) The precursor slurry obtained in the step (2) is spray-dried, and granulated at 280 ° C to obtain a precursor powder;
(4)将步骤(3)得到的前驱体粉体于900℃焙烧6小时，冷却后即得到所述碳纳米纤维改性钛酸锂。(4) The precursor powder obtained in the step (3) was baked at 900 ° C for 6 hours, and after cooling, the carbon nanofiber-modified lithium titanate was obtained.
经过恒电流充放电测试，结果表明该材料制成的负极在1C下的电化学容量达到172mAh g-1，在100C下容量能够到130mAh g-1。After constant current charge-discharge test results showed that the negative electrode material is made of the electrochemical capacity at 1C reached 172mAh g -1, the capacity can be at 100C to 130mAh g -1.
实施例12Example 12
本实施例与实施例11的不同之处在于：所述导电剂为改性碳纳米管，改性碳纳米管的制备方法步骤如下：The difference between this embodiment and the embodiment 11 is that the conductive agent is a modified carbon nanotube, and the steps of preparing the modified carbon nanotube are as follows:
(1)将碳纳米管、质量浓度45％的二甲基甲酰胺溶液及酸溶液按照1g：15mL：12mL的料液比混合，控制温度在38℃左右下搅拌混合40min，过滤，分别用水和无水乙醇洗涤，95℃下真空干燥60min得初级改性碳纳米管；所述酸溶液为质 量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1.2:1的体积比的混合物；(1) Mixing carbon nanotubes, 45% by mass of dimethylformamide solution and acid solution according to the ratio of material to liquid of 1g: 15mL: 12mL, and controlling the temperature to be stirred and mixed for about 40 minutes at about 38 ° C, filtering, respectively, using water and Washing with absolute ethanol, vacuum drying at 95 ° C for 60 min to obtain primary modified carbon nanotubes; the acid solution is qualitative a mixture of concentrated nitric acid having a concentration of 70% and concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1.2:1;
(2)将初级改性碳纳米管与化学剪切液按照1g：45mL的料液比混合，加热至160℃，水热反应55h，冷却，水洗，得次级改性碳纳米管；所述化学剪切液为浓度0.65moL/L的钼酸钠溶液与浓度0.4moL/L的硅钼酸溶液按照1:1的体积比的混合物；(2) mixing the primary modified carbon nanotubes with the chemical shear liquid according to a ratio of material to liquid of 1 g: 45 mL, heating to 160 ° C, hydrothermal reaction for 55 h, cooling, and washing with water to obtain secondary modified carbon nanotubes; The chemical shear solution is a mixture of a sodium molybdate solution having a concentration of 0.65 mol/L and a silicomolybdic acid solution having a concentration of 0.4 mol/L in a volume ratio of 1:1;
(3)次级改性碳纳米管与质量浓度60％的高氯酸按照1g：30mL的料液比混合均匀，加热至70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管。(3) The secondary modified carbon nanotubes and the perchloric acid with a mass concentration of 60% are uniformly mixed according to the ratio of material to liquid of 1g: 30mL, heated to 70 ° C for 24 hours, cooled, filtered, washed with water, and modified after vacuum drying. Carbon nanotubes.
将本发明实施例1～12中的负极浆料分别经涂布、碾压、冲切、叠片、注液和化成工艺后，制成相同规格的钛酸锂混合型电容器，对其进行内阻、循环寿命以及能量密度等性能参数的测定，实验结果见表1所示。The negative electrode slurry of the first to the second embodiments of the present invention is coated, rolled, punched, laminated, injected, and formed into a lithium titanate hybrid capacitor of the same specification. The performance parameters such as resistance, cycle life and energy density were measured. The experimental results are shown in Table 1.
表1Table 1
Figure PCTCN2015087660-appb-000001
Figure PCTCN2015087660-appb-000001
从上表可以看出，通过本发明的方法制备所得的钛酸锂负极浆料电容器具有较高的能量密度和突出的电化学性能，说明本发明得到的浆料均一性与稳定性好，有利于提高电容器的电化学性能。It can be seen from the above table that the obtained lithium titanate negative electrode slurry capacitor prepared by the method of the invention has high energy density and outstanding electrochemical performance, indicating that the slurry obtained by the invention has good uniformity and stability, and It is beneficial to improve the electrochemical performance of the capacitor.
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 (11)

  1. 一种混合型电容器负极浆料制备方法，其特征在于，包括以下步骤：A method for preparing a hybrid capacitor anode slurry, comprising the steps of:
    (1)按以下质量百分比称取各原料：5～10％导电剂，3～5％分散剂，3～5％粘结剂，80～89％钛酸锂，上述各组分质量百分比之和为100％；同时称取质量为导电剂、分散剂、粘结剂和钛酸锂总质量40～60％的去离子水；(1) Weigh each raw material by the following mass percentage: 5-10% conductive agent, 3~5% dispersant, 3~5% binder, 80-89% lithium titanate, the sum of the mass percentages of the above components 100%; at the same time weigh the conductive agent, dispersant, binder and lithium titanate total mass of 40 ~ 60% of deionized water;
    (2)向占总水量40～60％的去离子水中加入分散剂，搅拌均匀后静置12～24h，得分散母液；(2) adding a dispersing agent to deionized water containing 40 to 60% of the total water amount, stirring uniformly, and then standing for 12 to 24 hours to obtain a dispersion mother liquid;
    (3)在分散母液中加入导电剂后在真空条件下搅拌0.5～1h，待物料冷却至室温时加入钛酸锂并以相同条件搅拌0.5～1h，待物料冷却至室温时加入粘结剂和剩余的去离子水，以相同条件搅拌0.5～1h后将物料冷却至室温，得混合浆料；(3) adding conductive agent to the dispersion mother liquid and stirring under vacuum for 0.5 to 1 h. When the material is cooled to room temperature, lithium titanate is added and stirred under the same conditions for 0.5 to 1 h, and the binder is added after the material is cooled to room temperature. The remaining deionized water is stirred under the same conditions for 0.5 to 1 hour, and then the material is cooled to room temperature to obtain a mixed slurry;
    (4)对混合浆料进行高速分散20～35min即得混合型电容器负极浆料。(4) The mixed slurry is subjected to high-speed dispersion for 20 to 35 minutes to obtain a mixed capacitor negative electrode slurry.
  2. 根据权利要求1所述的一种混合型电容器负极浆料制备方法，其特征在于，所述导电剂为导电炭黑和石墨烯的混合物，或导电碳黑、碳纳米管与石墨烯的混合物。The method for preparing a hybrid capacitor anode slurry according to claim 1, wherein the conductive agent is a mixture of conductive carbon black and graphene, or a mixture of conductive carbon black, carbon nanotubes and graphene.
  3. 根据权利要求2所述的一种混合型电容器负极浆料制备方法，其特征在于，导电碳黑与石墨烯的质量比为(3～5):(1～3)，导电碳黑、碳纳米管与石墨烯的质量比为(2～4)：(1～3)：(1～3)。The method for preparing a hybrid capacitor anode slurry according to claim 2, wherein the mass ratio of the conductive carbon black to the graphene is (3 to 5): (1 to 3), conductive carbon black, carbon nanometer. The mass ratio of the tube to the graphene is (2 to 4): (1 to 3): (1 to 3).
  4. 根据权利要求1所述的一种混合型电容器负极浆料制备方法，其特征在于，所述分散剂为羧甲基纤维素钠，所述粘结剂为SBR乳液。The method of preparing a hybrid capacitor anode slurry according to claim 1, wherein the dispersing agent is sodium carboxymethylcellulose, and the binder is an SBR emulsion.
  5. 根据权利要求1所述的一种混合型电容器负极浆料制备方法，其特征在于，步骤(3)中真空条件下搅拌的工艺参数为：真空度为0.09～0.1MPa，搅拌速率为100～250r/min；步骤(7)中高速分散时的转速为3000～8000r/min。The method for preparing a mixed capacitor negative electrode slurry according to claim 1, wherein the process parameter of the stirring under the vacuum condition in the step (3) is: a vacuum degree of 0.09 to 0.1 MPa, and a stirring rate of 100 to 250 r. /min; The rotation speed at the time of high-speed dispersion in the step (7) is 3,000 to 8000 r/min.
  6. 根据权利要求1所述的一种混合型电容器负极浆料制备方法，其特征在于，所述钛酸锂为碳纳米纤维改性钛酸锂，所述钛酸锂颗粒均匀分布于所述碳纳米纤维的表面和内部，碳纳米纤维上负载的钛酸锂颗粒占碳纳米纤维改性钛酸锂总质量的15～18％。The method for preparing a hybrid capacitor anode slurry according to claim 1, wherein the lithium titanate is carbon nanofiber-modified lithium titanate, and the lithium titanate particles are uniformly distributed in the carbon nanometer. On the surface and inside of the fiber, the lithium titanate particles supported on the carbon nanofibers account for 15 to 18% of the total mass of the carbon nanofiber-modified lithium titanate.
  7. 根据权利要求6所述的一种混合型电容器负极浆料制备方法，其特征在于所述碳纳米纤维改性钛酸锂的制备方法如下：(1)将碳纳米纤维在异丙醇中充分分散，制备出碳纳米纤维的浆料；The method for preparing a hybrid capacitor anode slurry according to claim 6, wherein the carbon nanofiber-modified lithium titanate is prepared as follows: (1) the carbon nanofibers are sufficiently dispersed in isopropyl alcohol. Preparing a slurry of carbon nanofibers;
    (2)按照锂元素与钛元素摩尔比为3.5～4.5:5的比例分别称取碳酸锂与二氧 化钛，将其加入到步骤(1)制得的浆料中，充分混合，得到前驱体浆料；(2) Weigh lithium carbonate and dioxane according to the ratio of lithium element to titanium element molar ratio of 3.5 to 4.5:5 Titanium, added to the slurry prepared in the step (1), and thoroughly mixed to obtain a precursor slurry;
    (3)将步骤(2)得到的前驱体浆料进行喷雾干燥造粒，得到前驱体粉体；(3) the precursor slurry obtained in the step (2) is spray-dried and granulated to obtain a precursor powder;
    (4)将步骤(3)得到的前驱体粉体于800～900℃焙烧1～10小时，冷却后即得到所述碳纳米纤维改性钛酸锂。(4) The precursor powder obtained in the step (3) is calcined at 800 to 900 ° C for 1 to 10 hours, and after cooling, the carbon nanofiber-modified lithium titanate is obtained.
  8. 根据权利要求1所述的一种混合型电容器负极浆料制备方法，其特征在于，所述导电剂为改性碳纳米管，改性碳纳米管的制备方法步骤如下：The method for preparing a hybrid capacitor anode slurry according to claim 1, wherein the conductive agent is a modified carbon nanotube, and the steps of preparing the modified carbon nanotube are as follows:
    (1)将碳纳米管、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：10-20mL：5-15mL的料液比混合，控制温度35-45℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，80-100℃下真空干燥30-60min得初级改性碳纳米管；(1) mixing carbon nanotubes, a concentration of 30-50% dimethylformamide solution and an acid solution according to a ratio of material to liquid of 1g: 10-20mL: 5-15mL, and mixing and controlling at a temperature of 35-45 ° C. -50min, filtration, washing with water and anhydrous ethanol, vacuum drying at 80-100 ° C for 30-60min to obtain primary modified carbon nanotubes;
    (2)将初级改性碳纳米管与化学剪切液按照1g：30-50mL的料液比混合，加热至150-180℃，水热反应40-60h，冷却，水洗，得次级改性碳纳米管；(2) mixing the primary modified carbon nanotubes with the chemical shear liquid according to the ratio of material to liquid of 1g: 30-50mL, heating to 150-180 ° C, hydrothermal reaction for 40-60 hours, cooling, washing with water to obtain secondary modification. Carbon nanotubes;
    (3)次级改性碳纳米管与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至60-70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管。(3) The secondary modified carbon nanotubes and the perchloric acid having a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 60-70 ° C for 24 hours, cooled, filtered, washed with water, The modified carbon nanotubes are obtained after vacuum drying.
  9. 根据权利要求8所述的一种混合型电容器负极浆料制备方法，其特征在于：所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1-2:1的体积比的混合物。The method for preparing a hybrid capacitor anode slurry according to claim 8, wherein the acid solution is a concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume of 1-2:1. a mixture of ratios.
  10. 根据权利要求8所述的一种混合型电容器负极浆料制备方法，其特征在于：所述化学剪切液为浓度0.5-0.8moL/L的钼酸钠溶液与浓度0.3-0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。The method for preparing a hybrid capacitor negative electrode slurry according to claim 8, wherein the chemical shearing solution is a sodium molybdate solution having a concentration of 0.5-0.8 moL/L and a concentration of 0.3-0.5 moL/L. A mixture of silicomolybdic acid solution in a volume ratio of 1:1.
  11. 一种采用权利要求1所述的混合型电容器负极浆料的混合型电容器。 A hybrid capacitor using the hybrid capacitor negative electrode slurry according to claim 1.
PCT/CN2015/087660 2014-12-12 2015-08-20 Preparation method for mixed capacitor negative electrode slurry WO2016090958A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410766521.8A CN104681306A (en) 2014-12-12 2014-12-12 Preparation method for mixed capacitor cathode pulp
CN201410766521.8 2014-12-12

Publications (1)

Publication Number Publication Date
WO2016090958A1 true WO2016090958A1 (en) 2016-06-16

Family

ID=53316221

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/087660 WO2016090958A1 (en) 2014-12-12 2015-08-20 Preparation method for mixed capacitor negative electrode slurry

Country Status (4)

Country Link
CN (1) CN104681306A (en)
AU (1) AU2015100977A4 (en)
DE (1) DE102015121585A1 (en)
WO (1) WO2016090958A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104681306A (en) * 2014-12-12 2015-06-03 宁波南车新能源科技有限公司 Preparation method for mixed capacitor cathode pulp
CN106935804A (en) * 2015-12-31 2017-07-07 深圳市沃特玛电池有限公司 The preparation method and lithium ion battery of a kind of lithium titanate cathode size
CN108470636A (en) * 2018-02-07 2018-08-31 宁波中车新能源科技有限公司 A kind of Graphene electrodes piece and preparation method thereof and the method for preparing ultracapacitor with it
CN108470635A (en) * 2018-02-07 2018-08-31 宁波中车新能源科技有限公司 A kind of low internal resistance, high power graphene super capacitor electrode slice and preparation method thereof
CN109950505B (en) * 2019-04-02 2022-06-28 上海玖银电子科技有限公司 Lithium titanate battery slurry and preparation method thereof
WO2023117491A1 (en) * 2021-12-23 2023-06-29 Skeleton Technologies GmbH Energy storage cells with fast charge and discharge capabilites
WO2023117492A2 (en) 2021-12-23 2023-06-29 Skeleton Technologies GmbH Electrode material compositions for electrodes of energy storage cells with fast charge and discharge capabilities

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1807233A (en) * 2006-01-26 2006-07-26 上海交通大学 Chemical shearing method for preparing high dispersion short carbon nanometer tube
CN103177882A (en) * 2013-03-21 2013-06-26 苏州大学 Negative plate for lithium ion capacitor 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
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
CN103887556A (en) * 2014-03-13 2014-06-25 深圳格林德能源有限公司 Power energy storage polymer lithium ion battery and preparation method thereof
CN104393272A (en) * 2014-10-22 2015-03-04 中国石油大学(北京) Lithium titanate cathode composite material and preparation method
CN104681306A (en) * 2014-12-12 2015-06-03 宁波南车新能源科技有限公司 Preparation method for mixed capacitor cathode pulp

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007294654A (en) * 2006-04-25 2007-11-08 Gs Yuasa Corporation:Kk Electrochemical capacitor
CN104017520B (en) * 2014-05-27 2016-06-01 中国科学院广州能源研究所 Terpine resin base water-based binder and the application in lithium ion battery negative or ultracapacitor thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1807233A (en) * 2006-01-26 2006-07-26 上海交通大学 Chemical shearing method for preparing high dispersion short carbon nanometer tube
CN103177882A (en) * 2013-03-21 2013-06-26 苏州大学 Negative plate for lithium ion capacitor and preparation method thereof
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
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
CN103887556A (en) * 2014-03-13 2014-06-25 深圳格林德能源有限公司 Power energy storage polymer lithium ion battery and preparation method thereof
CN104393272A (en) * 2014-10-22 2015-03-04 中国石油大学(北京) Lithium titanate cathode composite material and preparation method
CN104681306A (en) * 2014-12-12 2015-06-03 宁波南车新能源科技有限公司 Preparation method for mixed capacitor cathode pulp

Also Published As

Publication number Publication date
AU2015100977A4 (en) 2015-09-17
DE102015121585A1 (en) 2016-06-16
CN104681306A (en) 2015-06-03

Similar Documents

Publication Publication Date Title
Liu et al. Hierarchical flower-like C/NiO composite hollow microspheres and its excellent supercapacitor performance
WO2016090958A1 (en) Preparation method for mixed capacitor negative electrode slurry
Du et al. Strategies to succeed in improving the lithium-ion storage properties of silicon nanomaterials
Zhang et al. Three-dimensional pompon-like MnO2/graphene hydrogel composite for supercapacitor
Zhao et al. Three-dimensionally interconnected Co9S8/MWCNTs composite cathode host for lithium–sulfur batteries
WO2016107239A1 (en) Hybrid supercapacitor
WO2015139660A1 (en) Porous carbon nanotube microsphere and preparation method therefor and application thereof, lithium metal-skeleton carbon composite material and preparation method therefor, negative electrode, and battery
US10312519B2 (en) Method for manufacturing electroconductive paste, and electroconductive paste
CN107492661B (en) Graphene lithium battery conductive slurry and preparation method thereof
CN108598414B (en) Amorphous zinc oxide/carbon composite lithium ion battery cathode material and preparation method thereof
Qi et al. Aqueous slurry of S-doped carbon nanotubes as conductive additive for lithium ion batteries
WO2016095559A1 (en) Method for dispersing composite conductive agent in electrode slurry of lithium ion capacitor
WO2017031943A1 (en) Method for preparing negative electrode paste for high-capacity silica-powder-doped lithium battery
KR20070030274A (en) Nanocarbon composite structure having ruthenium oxide trapped therein
Ihsan et al. V2O5/mesoporous carbon composite as a cathode material for lithium-ion batteries
WO2013010346A1 (en) Lithium-ion battery negative electrode-use silicon-carbon composite material and preparation method therefor
CN113035407B (en) Carbon nano tube compound conductive slurry for lithium ion battery and preparation method thereof
Li et al. Fabrication of porous carbon-coated ZnO nanoparticles on electrochemical exfoliated graphene as an anode material for lithium-ion batteries
JP2013077479A (en) Conductive auxiliary agent dispersion liquid for electrode material of lithium ion secondary battery
Li et al. Metal-organic framework-derived Mn3O4 nanostructure on reduced graphene oxide as high-performance supercapacitor electrodes
CN113659125B (en) Silicon-carbon composite material and preparation method thereof
WO2017036350A1 (en) Lithium ion battery negative electrode material and preparation method thereof and lithium ion battery
WO2016110108A1 (en) Method of preparing plasma spraying for nanoscale lithium-ion composite positive electrode
CN106025228A (en) Nanocomposite loading carbon-coated SnO2 nano particles on graphene sheets and preparation method of nanocomposite
Wang et al. MoO 2/C hollow nanospheres synthesized by solvothermal method as anode material for lithium-ion batteries

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15866884

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15866884

Country of ref document: EP

Kind code of ref document: A1