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WO2018113486A1 - 锂离子电池浆料及其制备方法 - Google Patents

锂离子电池浆料及其制备方法 Download PDF

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Publication number
WO2018113486A1
WO2018113486A1 PCT/CN2017/113399 CN2017113399W WO2018113486A1 WO 2018113486 A1 WO2018113486 A1 WO 2018113486A1 CN 2017113399 W CN2017113399 W CN 2017113399W WO 2018113486 A1 WO2018113486 A1 WO 2018113486A1
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Prior art keywords
slurry
mixed
active material
ion battery
lithium
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English (en)
French (fr)
Inventor
付容
祝佳丽
李双喜
余志文
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Shenzhen Topband Co Ltd
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Shenzhen Topband Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention relates to the field of lithium ion battery technology, and more particularly to a lithium ion battery slurry and a method of preparing the same.
  • Lithium-ion batteries have been rapidly advancing in the battery market due to their high output voltage, high specific energy and long life. Now battery manufacturers are expanding their production scale. In the current mature lithium batteries, governments of all countries pay more attention to production and product use, and continue to expand the new energy market. In order to allow new energy sources to continue to develop, there are strict requirements for the use of lithium-ion batteries.
  • Pulping provides electrode slurry, which is the first step in the production process of lithium batteries, and is also the most important link.
  • the conventional preparation process of the existing lithium ion battery has the disadvantages of complicated process, long production cycle, and low production efficiency. technical problem
  • the technical problem to be solved by the present invention is to provide a method for preparing a lithium ion battery slurry having a simple process, a short production cycle, and a good slurry quality, and a method for preparing the same according to the above-mentioned defects of the prior art. Lithium ion battery slurry.
  • the technical solution adopted by the present invention to solve the technical problem thereof is: Constructing a preparation method of a lithium ion battery slurry, comprising the following steps:
  • S10, the active material, the binder and the conductive agent are iron-removed and then put into a double-shaft paddle type high-efficiency mixer, and the mixture is evenly mixed to form a mixed powder;
  • the mixed slurry is put into a high-speed disperser for high-speed dispersion to form a semi-finished slurry having a solid content of 70-80%;
  • the present invention also provides a method for preparing a lithium ion battery slurry, comprising the following steps:
  • S10, the active material, the binder and the conductive agent are iron-discharged together with the solvent into a two-axis paddle type high-efficiency mixer, and uniformly mixed to form a premixed slurry;
  • the mixing time is 3-5 minutes.
  • step S10 the active material, the binder and the conductive agent are de-ironed by a iron remover, and the removal of the iron is less than 30 minutes.
  • the mixed slurry of step S20 is mixed and formed in a mixer, the mixer revolution speed is ⁇ 15r/min, the rotation speed is ⁇ 1000]"/1 ⁇ , and the mixing and mixing time is ⁇ 60 minutes.
  • step S30 the linear velocity of the high-speed dispersion is 66 m/s, and the temperature of the slurry is controlled during the dispersion process.
  • the defoaming time under vacuum is 10-30 minutes, and the degree of vacuum is ⁇ -0.08 Mpa.
  • the active material is a positive electrode active material or a negative electrode active material
  • the solvent is N-methylpyrrolidone or deionized water.
  • the positive active material is lithium cobalt oxide (LiCo0 2 ), lithium nickel oxide (LiNi0 2 ), lithium manganese oxide (LiMn 2 0 4 ), manganese nickel cobalt composite oxide (LiMn x Ni y Co lxy O 2 ) , one or more of lithium vanadium oxide (LiV 2 0 4 ) or lithium iron oxide (LiFeP0 2 );
  • the negative active material is artificial graphite, natural graphite or mesophase carbon One or more of the microspheres, wherein x, y, X + y are both greater than 0 and less than 1;
  • the binder is one or more of polyvinyl alcohol, polyvinylidene fluoride, vinylidene fluoride, polytetrafluoroethylene, hexafluoropropylene, acrylate, polyurethane, sodium carboxymethyl cellulose
  • the conductive agent is one or more of conductive carbon black, conductive graphite, carbon fiber, and carbon nanotube.
  • the present invention also provides a lithium ion battery slurry which is obtained by the above preparation method.
  • the present invention shortens the intermixing process of the pulping process by dry mixing or wet mixing of all raw materials using a biaxial paddle type high-efficiency mixer; dispersing the wet powder by a high-speed dispersing machine to obtain quality Good slurry, simplifying the process, easy to operate and easy to produce; shortening the preparation time and helping to improve production efficiency.
  • FIG. 1 is a flow chart showing a method for preparing a lithium ion battery slurry according to Embodiment 1 of the present invention
  • FIG. 2 is a flow chart of a method for preparing a lithium ion battery slurry according to Embodiment 2 of the present invention
  • FIG. 3 is a schematic view of an apparatus used in a method for preparing a lithium ion battery slurry of the present invention
  • FIG. 4 is a comparison of slurry viscosity of a lithium ion battery slurry prepared by the method of the present invention and a prior art method; [0029] FIG.
  • FIG. 5 is a comparison diagram of solid content of a lithium ion battery slurry prepared by the method of the present invention and a prior art method, and a preferred embodiment for carrying out the invention. [0030] FIG.
  • a method for preparing a lithium ion battery slurry of the present invention comprises the following steps:
  • S10, the active material, the binder and the conductive agent are iron-removed, and then put into a double-shaft paddle type high-efficiency mixer, and the mixture is evenly mixed to form a mixed powder.
  • the active material is a positive electrode active material or a negative electrode active material
  • the solvent is N-methylpyrrolidone or deionized water.
  • the positive electrode active material is lithium cobalt oxide (LiCo0 2 ), lithium nickel oxide (LiNiO 2 ), lithium manganese oxide (LiMn 2 0 4 ), manganese nickel cobalt composite oxide (LiMn x Ni y Co lxy O 2 ) one or more of lithium vanadium oxide (LiV 2 0 4 ) or lithium iron oxide (LiFeP0 2 ), wherein x, y and x+y are both greater than 0 and less than 1.
  • the anode active material is one or more of artificial graphite, natural graphite or mesocarbon microbeads.
  • the binder is one or more of polyvinyl alcohol, polyvinylidene fluoride, vinylidene fluoride, polytetrafluoroethylene, hexafluoropropylene, acrylate, polyurethane, sodium carboxymethylcellulose.
  • the conductive agent is one or more of conductive carbon black, conductive graphite, carbon fiber, and carbon nanotube.
  • the active material, the binder and the conductive agent after the iron removal by the iron remover are all put into the double-shaft paddle type high-efficiency mixer at one time, and all the dry powders use the double-axis paddles.
  • the high-efficiency mixer performs a one-time dry mixing process to form a mixed powder. In addition to the shovel ⁇ 30 minutes, the mixing time is 3-5 minutes.
  • the two-axis paddle type high-efficiency mixer has two rotors with opposite rotation directions, the rotor is composed of a rotor shaft, a strut, and a blade, and the strut intersects the rotor shaft "cross", and the blade is welded at a special angle. On the pole.
  • the blade material on the rotor rotates along the inner wall of the machine groove and moves toward one end, and on the other hand, the animal material is turned to the left and right; at the intersection of the two rotors, a weight loss zone is formed, in which the material is The shape, size and density can make the material float up, and it is in the state of instantaneous weight loss, so that the material forms a continuous cycle in the machine slot and interlaces with each other to achieve the effect of rapid mixing and uniformity.
  • the amount of the solvent is appropriately added according to the solid content requirement.
  • the solvent is N-methylpyrrolidone or deionized water.
  • the active material is a positive electrode active material ⁇
  • the solvent is preferably N-methylpyrrolidone
  • the active material is a negative electrode active material ⁇
  • the solvent is preferably deionized water.
  • the mixed slurry of step S20 is mixed and formed in a mixer, the mixer revolution speed is ⁇ 15r/min, the rotation speed is ⁇ 10003" /min, and the mixing and mixing time is ⁇ 60 minutes.
  • the mixed slurry is put into a high-speed disperser for high-speed dispersion to form a semi-finished product having a solid content of 70-80%.
  • the linear velocity of the high-speed dispersion is 66 m/s, and the temperature of the slurry is controlled to be 20 to 45 during the dispersion process.
  • the mixed slurry obtained in the step S20 is subjected to high-speed stirring and dispersion, so that the powder is completely dispersed, and a uniformly dispersed slurry is obtained.
  • the high-speed dispersing machine adopts stepless speed regulation: there are various forms such as electromagnetic speed regulation, frequency conversion speed regulation and explosion-proof frequency conversion speed regulation.
  • the dispersing disc of the high-speed dispersing machine is laminar under the dispersing disc, and the slurry layers of different flow rates are mutually diffused to play a dispersion role.
  • the high-speed high-speed dispersing machine has various functions such as hydraulic lifting, 360-degree rotation, stepless speed regulation, etc.
  • the slurry has a rolling annular flow, which produces a strong vortex. The particles on the surface of the slurry spiral down to the bottom of the vortex.
  • the high-speed disperser forms a turbulent zone at the edge of the dispersion disc, and the slurry and particles are strongly sheared and impacted.
  • the upper and lower beams are formed outside the area, and the slurry is fully circulated and flipped. It can be changed from one cylinder to another in a short space, which greatly improves the work efficiency and reduces the labor. Strength, a highly dispersible slurry can be obtained.
  • the defoaming time under vacuum is 10-30 minutes, and the degree of vacuum is ⁇ -0.08 Mpa.
  • the amount of the raw materials such as the active material, the conductive agent and the binder is weighed according to the ratio of the raw materials of the positive electrode slurry or the negative electrode slurry of the lithium ion battery, and the ratio of the materials in the prior art can be used. .
  • a method for preparing a lithium ion battery slurry of the present invention comprises the following steps:
  • the mixture is uniformly mixed to form a premixed slurry.
  • the mixing time is 3-5 minutes, and the mixing time is 3-5 minutes.
  • the active material, the binder and the conductive agent are iron-removed by the iron remover, and then all of them are put into the two-axis paddle type high-efficiency mixer together with the solvent, and all the dry powder and the solvent are used in the two-axis.
  • the paddle type high efficiency mixer performs a one-time wet mixing process to form a premixed slurry.
  • the solvent is appropriately added according to the solid content requirement.
  • the solvent is N-methylpyrrolidone or deionized water.
  • the active material is a positive electrode active material ⁇
  • the solvent is preferably N-methylpyrrolidone
  • the active material is a negative electrode active material ⁇
  • the solvent is preferably deionized water.
  • step S20 The premixed slurry is stirred to be uniformly mixed to form a mixed slurry.
  • the mixed slurry of step S20 is mixed and formed in a mixer, and the mixer revolution speed is ⁇ 151" /!! 1 1 1, the rotation speed is ⁇ ..!/!, the mixing and mixing time is ⁇ 60 minute.
  • the mixed slurry is put into a high-speed disperser for high-speed dispersion to form a semi-finished product having a solid content of 70-80%.
  • the linear velocity of the high-speed dispersion is 66 m/s, and the temperature of the slurry is controlled to be 20 to 45 ° C during the dispersion process. If necessary, the slurry is heated to a higher temperature. The homogenate is wiped with alcohol or added. Cool the water or reduce the speed, the discharge viscosity is 2900-8000MPa. S. In this step, the mixed slurry obtained in the step S20 is subjected to high-speed stirring and dispersion, so that The powder is completely dispersed to form a uniformly dispersed slurry.
  • the semi-finished slurry is defoamed under vacuum and sieved to form a lithium ion battery slurry.
  • the bubble is 10-30 minutes under vacuum, and the vacuum degree is ⁇ -0.08Mpa.
  • the amount of the raw materials such as the active material, the conductive agent and the binder is weighed according to the ratio of the raw materials of the positive electrode slurry or the negative electrode slurry of the lithium ion battery, and the ratio can be achieved by using the ratio in the prior art. .
  • the lithium ion battery slurry of the present invention is obtained by the above-described production method.
  • the active material used is a positive electrode active material
  • a lithium ion battery positive electrode slurry can be prepared, and the lithium ion battery positive electrode slurry can be used to form a pole piece as a positive electrode sheet of a lithium ion battery;
  • the active material used is a negative electrode active material
  • the lithium ion battery negative electrode slurry can be prepared, and the lithium ion battery negative electrode slurry can be used to form a pole piece as a negative electrode piece of a lithium ion battery.
  • the pole piece was fabricated, and the lithium ion battery slurry prepared above was coated on an aluminum foil and dried.
  • the positive electrode sheet and the negative electrode sheet and the separator are stacked and wound into a core, and the core is placed in an aluminum shell to inject an electrolyte
  • Embodiment 1 With reference to FIG. 3, the preparation process of Embodiment 1 is as follows:
  • control slurry temperature is 20 ⁇ 45 ° C, necessary ⁇ (slurry temperature is higher ⁇ ) wipe the homogenizer with alcohol or add cooling water or reduce the speed, discharge viscosity 2900-8000MPa.
  • S solid content is 70 ⁇ 80 % ;
  • step b The slurry after completion of step b is dispersed by a high-speed disperser 7, at a rotational speed of 14,000 rpm, and a linear velocity of 66 m/s.
  • the temperature of the slurry to 20 ⁇ 45°C, necessary ⁇ (higher temperature of the slurry). Wipe the homogenizer with alcohol or add cooling water or reduce the rotation speed.
  • the viscosity of the discharge is 2900-8000MPa.s, solid content 70 ⁇ 80 ⁇ 3 ⁇ 4;
  • FIG. 4 is a graph showing the viscosity of the slurry of Examples 1, 2 and Comparative Example 1 of the present invention
  • FIG. 5 is a solid content of the slurry of Examples 1, 2 and Comparative Example 1 of the present invention. Comparing the figures, it can be seen from Fig. 4 and Fig. 5 that the viscosity and solid content of the slurry prepared by the invention are more stable, the quality is better, and the quality of the lithium ion battery slurry product is improved.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

一种锂离子电池浆料及其制备方法,所述锂离子电池浆料的制备方法包括以下步骤:S10、将活性材料、粘结剂和导电剂除铁后投入双轴桨叶式高效混合机中,混合均匀,形成混合粉体;或者,将活性材料、粘结剂和导电剂除铁后与溶剂一起投入双轴桨叶式高效混合机中,混合均匀,形成预混浆料;S20、在所述混合粉体中加入溶剂,搅拌以混合均匀,形成混合浆料;或者,将所述预混浆料搅拌以混合均匀,形成混合浆料;S30、将所述混合浆料投入高速分散机中进行高速分散,形成固含量为70‑80%的半成品浆料;S40、将所述半成品浆料真空下除泡,过筛,形成锂离子电池浆料。该制备方法简化了工艺流程、易于操作便于生产;缩短了制备时间、有助于提高生产效率。

Description

说明书 发明名称:锂离子电池浆料及其制备方法 技术领域
[0001] 本发明涉及锂离子电池技术领域, 更具体地说, 涉及一种锂离子电池浆料及其 制备方法。
背景技术
[0002] 近年来新能源一直是国家最为重视的项目, 而锂离子电池因输出电压高, 比能 量高、 寿命长, 在电池市场中得到了快速推进, 现电池厂家幵始不断扩大生产 规模。 在目前较为成熟的锂电池中, 各国政府对生产、 产品使用都较为重视, 不断扩大新能源市场, 为让新能源持续发展, 对锂离子电池的使用有严格要求
[0003] 制浆提供电极浆液, 是锂电池生产过程首瑞环节, 也是最重要环节。 现有锂离 子电池的传统制备工艺方法存在工艺复杂、 制作周期长、 生产效率低等缺点。 技术问题
[0004] 本发明要解决的技术问题在于, 针对现有技术的上述缺陷, 提供一种工艺简单 、 生产周期短、 浆料质量好的锂离子电池浆料的制备方法及使用该制备方法制 得的锂离子电池浆料。
问题的解决方案
技术解决方案
[0005] 本发明解决其技术问题所采用的技术方案是: 构造一种锂离子电池浆料的制备 方法, 包括以下步骤:
[0006] S10、 将活性材料、 粘结剂和导电剂除铁后投入双轴桨叶式高效混合机中, 混 合均匀, 形成混合粉体;
[0007] S20、 在所述混合粉体中加入溶剂, 搅拌以混合均匀, 形成混合浆料;
[0008] S30、 将所述混合浆料投入高速分散机中进行高速分散, 形成固含量为 70-80% 的半成品浆料;
[0009] S40、 将所述半成品浆料真空下除泡, 过筛, 形成锂离子电池浆料。 [0010] 本发明还提供一种锂离子电池浆料的制备方法, 包括以下步骤:
[0011] S 10、 将活性材料、 粘结剂和导电剂除铁后与溶剂一起投入双轴桨叶式高效混 合机中, 混合均匀, 形成预混浆料;
[0012] S20、 将所述预混浆料搅拌以混合均匀, 形成混合浆料;
[0013] S30、 将所述混合浆料投入高速分散机中进行高速分散, 形成固含量为 70-80% 的半成品浆料;
[0014] S40、 将所述半成品浆料真空下除泡, 过筛, 形成锂离子电池浆料。
[0015] 优选地, 步骤 S 10中, 混合吋间为 3-5分钟。
[0016] 优选地, 步骤 S 10中, 所述活性材料、 粘结剂及导电剂通过除铁器进行除铁, 除铁吋间≤30分钟。
[0017] 优选地, 步骤 S20的混合浆料在搅拌机中混合形成, 所述搅拌机公转速度≤15r/ min, 自转速度≤1000]"/1^^ 搅拌混合吋间≤60分钟。
[0018] 优选地, 步骤 S30中, 高速分散的线速度为 66m/s, 分散过程中控制浆料温度为
20~45。C。
[0019] 优选地, 步骤 S40中, 真空下除泡吋间为 10-30分钟, 真空度≥-0.08Mpa。
[0020] 优选地, 所述活性材料为正极活性材料或负极活性材料, 所述溶剂为 N-甲基吡 咯烷酮或去离子水。
[0021] 优选地, 所述正极活性材料为锂钴氧化物 (LiCo0 2) 、 锂镍氧化物 (LiNi0 2 ) 、 锂锰氧化物 (LiMn 20 4) 、 锰镍钴复合氧化物 (LiMn xNi yCo l x yO 2) 、 锂 钒氧化物 (LiV 20 4) 或锂铁氧化物 (LiFeP0 2) 中的一种或多种; 所述负极活 性材料为人造石墨、 天然石墨或中间相碳微球中的一种或多种, 其中, x、 y、 X +y均大于 0小于 1 ;
[0022] 所述粘结剂为聚乙烯醇、 聚偏氟乙烯、 偏二氟乙烯、 聚四氟乙烯、 六氟丙烯、 丙烯酸酯、 聚氨酯、 羧甲基纤维素钠中的一种或多种; 所述导电剂为导电炭黑 、 导电石墨、 碳纤维、 碳纳米管中的一种或多种。
[0023] 本发明还提供一种锂离子电池浆料, 采用上述的制备方法制得。
发明的有益效果
有益效果 [0024] 本发明的有益效果: 本发明通过将所有原料使用双轴桨叶式高效混合机进行干 混合或湿混合, 缩短制浆过程的吋间; 使用高速分散机分散湿粉料, 得到质量 好的浆料, 简化了工艺流程、 易于操作便于生产; 缩短了制备吋间、 有助于提 高生产效率。
对附图的简要说明
附图说明
[0025] 下面将结合附图及实施例对本发明作进一步说明, 附图中:
[0026] 图 1是本发明实施例一中锂离子电池浆料的制备方法的流程图;
[0027] 图 2是本发明实施例二中锂离子电池浆料的制备方法的流程图;
[0028] 图 3是本发明锂离子电池浆料的制备方法所用设备的示意图;
[0029] 图 4是采用本发明方法和现有技术方法制备的锂离子电池浆料的浆料粘度比较 图;
[0030] 图 5是采用本发明方法和现有技术方法制备的锂离子电池浆料的固含量比较图 实施该发明的最佳实施例
本发明的最佳实施方式
[0031] 为了对本发明的技术特征、 目的和效果有更加清楚的理解, 现对照附图详细说 明本发明的具体实施方式。
[0032] 实施例一
[0033] 参阅图 1, 本发明的锂离子电池浆料的制备方法, 包括以下步骤:
[0034] S 10、 将活性材料、 粘结剂和导电剂除铁后投入双轴桨叶式高效混合机中, 混 合均匀, 形成混合粉体。
[0035] 其中, 活性材料为正极活性材料或负极活性材料, 溶剂为 N-甲基吡咯烷酮或去 离子水。 优选地, 正极活性材料为锂钴氧化物 (LiCo0 2) 、 锂镍氧化物 (LiNiO 2) 、 锂锰氧化物 (LiMn 20 4) 、 锰镍钴复合氧化物 (LiMn xNi yCo l x yO 2) 、 锂 钒氧化物 (LiV 20 4) 或锂铁氧化物 (LiFeP0 2) 中的一种或多种, 其中, x、 y 、 x+y均大于 0小于 1。
[0036] 负极活性材料为人造石墨、 天然石墨或中间相碳微球中的一种或多种。 [0037] 粘结剂为聚乙烯醇、 聚偏氟乙烯、 偏二氟乙烯、 聚四氟乙烯、 六氟丙烯、 丙烯 酸酯、 聚氨酯、 羧甲基纤维素钠中的一种或多种。
[0038] 导电剂为导电炭黑、 导电石墨、 碳纤维、 碳纳米管中的一种或多种。
[0039] 具体的, 该步骤 S10中, 将通过除铁器除铁后的活性材料、 粘结剂和导电剂一 次性全部投入双轴桨叶式高效混合机中, 所有干粉体使用双轴桨叶式高效混合 机进行一次性干混合工艺, 形成混合粉体。 除铁吋间≤30分钟, 混合吋间为 3-5 分钟。
[0040] 由于双轴桨叶式高效混合机上有两个旋转方向相反的转子, 转子由转子轴、 支 杆、 桨叶组成, 支杆与转子轴"十字"相交, 桨叶成特殊角度焊在支杆上。 转子上 的桨叶带动物料一方面沿着机槽内壁旋转并向一端移动,另一方面带动物料左右 翻动; 在两转子的交叉重叠处, 形成了一个失重区, 在此区域内, 不论物料的 形状、 大小和密度如何, 都能使物料上浮, 处于瞬间失重状态, 使物料在机槽 内形成连续循环翻动, 相互交错剪切, 从而达到快速混合均匀的效果。
[0041] S20、 在混合粉体中加入溶剂, 搅拌以混合均匀, 形成混合浆料。
[0042] 该步骤 S20中, 溶剂的用量根据固含量要求适当添加。 优选地, 溶剂为 N-甲基 吡咯烷酮或去离子水。 当活性材料为正极活性材料吋, 溶剂优选为 N-甲基吡咯 烷酮; 活性材料为负极活性材料吋, 溶剂优选为去离子水。 优选地, 步骤 S20的 混合浆料在搅拌机中混合形成, 所述搅拌机公转速度≤15r/min, 自转速度≤10003" /min, 搅拌混合吋间≤60分钟。
[0043] S30、 将混合浆料投入高速分散机中进行高速分散, 形成固含量为 70-80%的半 成品装料。
[0044] 该步骤 S30中, 高速分散的线速度为 66m/s, 分散过程中控制浆料温度为 20~45
°C, 必要吋 (浆料升温较高吋) 用酒精擦拭匀浆锅或加冷却水或降低转速, 出料 粘度 2900-8000MPa.S。 本步骤将步骤 S20获得的混合浆料进行高速搅拌分散, 使 粉体被完全打散, 制成分散均匀的浆料。
[0045] 高速分散机采用无级调速: 有电磁调速、 变频调速及防爆变频调速等多种形式 。 高速分散机的分散盘下方呈层流状态, 不同流速的浆料层互相扩散, 起到分 散作用。 高速高速分散机具有液压升降、 360度回转、 无级调速等多种功能, 使 浆料呈滚动环状流, 产生强旋涡, 浆料表面粒子呈螺旋状下降到涡流底部; 高 速分散机在分散盘边缘处形成湍流区, 浆料及粒子受到强烈剪切及冲击。 区域 外形成上下两个束流, 浆料得到充分循环及翻动, 能够在很短的吋间内从一个 缸变换到另一个缸进行作业, 极大地提高了工作效率, 同吋也降低了人工劳动 强度, 能得到分散极佳的浆料。
[0046] S40、 将半成品浆料真空下除泡, 过筛, 形成锂离子电池浆料。
[0047] 该步骤中, 真空下除泡吋间为 10-30分钟, 真空度≥-0.08Mpa。 本步骤中优选地 使用搅拌机对步骤 S4高速分散形成的混合浆料进行抽真空除泡。
[0048] 上述制备方法中, 活性材料、 导电剂和粘结剂等原料用量根据锂离子电池正极 浆料或负极浆料各原料配比称取, 可采用现有技术中所设定配比实现。
[0049] 实施例二
[0050] 参阅图 2, 本发明的锂离子电池浆料的制备方法, 包括以下步骤:
[0051] S10、 将活性材料、 粘结剂和导电剂除铁后与溶剂一起投入双轴桨叶式高效混 合机中, 混合均匀, 形成预混浆料。 优选地, 除铁吋间≤30分钟, 混合吋间为 3- 5分钟。 具体的, 该步骤 S10中, 将活性材料、 粘结剂和导电剂通过除铁器除铁 后, 与溶剂一起一次性全部投入双轴桨叶式高效混合机中, 所有干粉体和溶剂 使用双轴桨叶式高效混合机进行一次性湿混合工艺, 形成预混浆料。
[0052] 溶剂的用料根据固含量要求适当添加。 优选地, 溶剂为 N-甲基吡咯烷酮或去离 子水。 当活性材料为正极活性材料吋, 溶剂优选为 N-甲基吡咯烷酮; 活性材料 为负极活性材料吋, 溶剂优选为去离子水。
[0053] S20、 将预混浆料搅拌以混合均匀, 形成混合浆料。 优选地, 步骤 S20的混合浆 料在搅拌机中混合形成, 搅拌机公转速度≤151"/!! 111, 自转速度^。。。!"/!!!!!!, 搅拌 混合吋间≤60分钟。
[0054] S30、 将混合浆料投入高速分散机中进行高速分散, 形成固含量为 70-80%的半 成品装料。
[0055] 该步骤 S30中, 高速分散的线速度为 66m/s, 分散过程中控制浆料温度为 20~45 °C, 必要吋 (浆料升温较高吋) 用酒精擦拭匀浆锅或加冷却水或降低转速, 出料 粘度 2900-8000MPa.S。 本步骤将步骤 S20获得的混合浆料进行高速搅拌分散, 使 粉体被完全打散, 制成分散均匀的浆料。
[0056] S40、 将半成品浆料真空下除泡, 过筛, 形成锂离子电池浆料。 该步骤中, 真 空下除泡吋间为 10-30分钟, 真空度≥-0.08Mpa。 本步骤中优选地使用搅拌机对步 骤 S4高速分散形成的混合浆料进行抽真空除泡。
[0057] 上述制备方法中, 活性材料、 导电剂和粘结剂等原料用量根据锂离子电池正极 浆料或负极浆料各原料配比称取, 可采用现有技术中所设定配比实现。
[0058] 本发明的锂离子电池浆料, 采用上述的制备方法制得。 当使用的活性材料为正 极活性材料吋可制备锂离子电池正极浆料, 使用该锂离子电池正极浆料可制成 极片, 作为锂离子电池的正极片; 当使用的活性材料为负极活性材料吋可制备 锂离子电池负极浆料, 使用该锂离子电池负极浆料可制成极片, 作为锂离子电 池的负极片。
[0059] 极片制作吋, 将上述制得的锂离子电池浆料涂覆在铝箔上, 烘干后即得。
[0060] 将正极片与负极片、 隔膜叠置后卷绕成卷芯, 将卷芯放入铝壳中, 注入电解液
, 封口, 制得锂离子电池。
[0061] 下面将以具体实施例和对比例来对本发明和现有技术进行比较。
[0062] 实施例 1
[0063] 结合图 3, 实施例 1的制备过程如下:
[0064] (a) 按配方比例 (正极活性材料 Α^^δ^ , 导电齐 iJ l.O^AO^ , 粘接齐 iJO.8%-2.
0%) 称取粉料, 分别加入对应罐中, 正极活性材料 1经过除铁器, 导电剂 2经过 除铁器, 粘接剂 3经过除铁器, 除铁吋间≤301^!1;
[0065] (b) 将三种粉体物料同吋下放在双轴桨叶式高效混合机 4中, 混合均匀, 混合 吋间 3-5min, 得到正极混合粉体;
[0066] (c) 将所有正极混合粉体加入搅拌机 6中, 按配方称出溶剂 5 (N-甲基吡咯烷 酮) , 将溶剂 5通过双轴桨叶式高效混合机 4加入搅拌机 6中湿混合, 设备公转速
Jt≤15rpm, 自转速度≤1000rpm,混合吋间≤600101;
[0067] (d) 完成 c步骤后的湿粉料通过高速分散机 7分散, 转速为 14000
rpm,线速度 66m/s; 控制浆料温度为 20~45°C, 必要吋 (浆料升温较高吋) 用酒精 擦拭匀浆锅或加冷却水或降低转速, 出料粘度 2900-8000MPa.S, 固含量为 70〜80 % ;
[0068] (e) 完成 d步骤高速分散的浆料使用搅拌机 6抽真空除泡, 真空度≥-0.08Mpa,抽 真空吋间 10-30min;
[0069] (f) 完成 e步骤后过筛 8出料, 完成浆料出在浆料罐 9中, 得到锂离子电池正极 装料。
[0070] 实施例 2
[0071] 结合图 3, 实施例 2的制备过程如下:
[0072] (a) 按配方比例 (正极活性材料 94<¾-98<¾, 导电剂 1.0<¾-4.0<¾, 粘接剂 0.8<¾-2.
0%) 称取粉料, 分别加入对应罐中, 正极活性材料 1经过除铁器, 导电剂 2经过 除铁器, 粘接剂 3经过除铁器, 将三种粉体物料和溶剂 5 (N-甲基吡咯烷酮) 同 吋下放在双轴桨叶式高效混合机 4中, 混合均匀, 混合吋间 3-5min, 得到正极预 混装料;
[0073] (b) 将所有正极预混浆料加入搅拌机 6中, 搅拌机设备公转速度为≤15^^1, 自 转速度≤1000rpm, 混合吋间≤600101;
[0074] (c) 完成 b步骤后的浆料通过高速分散机 7分散, 转速 14000 rpm,线速度 66m/s
; 控制浆料温度为 20~45°C, 必要吋 (浆料升温较高吋) 用酒精擦拭匀浆锅或加 冷却水或降低转速, 出料粘度 2900-8000MPa.s, 固含量 70〜80<¾;
[0075] (d) 将完成 c步骤高速分散的浆料使用搅拌机 6抽真空除泡, 真空度≥-0.08Mpa, 抽真空吋间 10-30min;
[0076] (e) 完成 f步骤后过筛 8出料, 完成浆料出在浆料罐 9中, 得到锂离子电池正极 装料。
[0077] 对比例 1
[0078] (a) 按质量比, 将 100%溶剂加入制胶锅内, 抽真空补氮气, 真空度 -0.08〜- 0.1 mpa, 氮气压力大于等于 O. lmpa,加入 0.9- 1.5%粘接剂, 搅拌 60min均匀后, 所述 搅拌转速慢速 30~40rpm+高速 1500~2000rpm; 得到胶液;
[0079] (b) 在胶液中加入 0.6-1.0%导电剂搅拌 60min, 所述搅拌转速慢速 30~40rpm+ 高速 1500~2000rpm,再抽真空 30min,真空度高于 -0.09Mpa, 粘度 400-1000MPa-s, 固含量 4.0〜5.0<¾; [0080] (c) 加入正极材料 (97.37%-98.07%) , 搅拌, 转速为 1500-2200r/min, 搅拌 吋间 120~150min, 再抽真空 30min, 真空度不高于 -0.09MPa; 浆料控制温度为 20 ~45°C, 必要吋 (浆料升温较高吋) 用酒精擦拭匀浆锅或加冷却水或降低转速, 出料粘度 2900-8000MPa.s, 固含量 70〜80<¾;
[0081] (d) 搅拌完成后的浆料过 150目滤网过滤, 获得锂离子电池正极浆料。
[0082] 实施例 1、 2和对比例 1的对比结果如下:
[0083] 1、 使用对比例工艺用吋 5.5h-6.0小吋, 而实施例用吋 2.5h-3.0h, 实施例相比对 比例制浆吋间可缩短一半, 因此本发明总的吋间优于传统 (对比例 1) 的制备方 法;
[0084] 2、 对比例 1制备过程中需打导电胶液, 而实施例 1和 2无需制胶; 对比例 1需上 料两次, 下料两次, 而实施例 1和 2只需上料一次, 下料一次, 其他均由设备系 统自动进行, 因此本发明工艺更加简单;
[0085] 3、 使用对比例 1需多次检验, 而实施例只做一次最终检査, 可提高工作效率, 降低人工劳动强度。
[0086] 参阅图 4和图 5, 图 4是本发明实施例 1、 2与对比例 1的浆料粘度对比图, 图 5是 本发明实施例 1、 2与对比例 1的浆料固含量对比图, 从图 4和图 5可以看出, 本发 明制备的浆料粘度、 固含量更稳定, 质量更优, 提高了锂离子电池浆料产品质
[0087] 可以理解的, 以上实施例仅表达了本发明的优选实施方式, 其描述较为具体和 详细, 但并不能因此而理解为对本发明专利范围的限制; 应当指出的是, 对于 本领域的普通技术人员来说, 在不脱离本发明构思的前提下, 可以对上述技术 特点进行自由组合, 还可以做出若干变形和改进, 这些都属于本发明的保护范 围; 因此, 凡跟本发明权利要求范围所做的等同变换与修饰, 均应属于本发明 权利要求的涵盖范围。

Claims

权利要求书
[权利要求 1] 一种锂离子电池浆料的制备方法, 其特征在于, 包括以下步骤:
S10、 将活性材料、 粘结剂和导电剂除铁后投入双轴桨叶式高效混合 机中, 混合均匀, 形成混合粉体;
S20、 在所述混合粉体中加入溶剂, 搅拌以混合均匀, 形成混合浆料
S30、 将所述混合浆料投入高速分散机中进行高速分散, 形成固含量 为 70-80%的半成品浆料;
S40、 将所述半成品浆料真空下除泡, 过筛, 形成锂离子电池浆料。
[权利要求 2] —种锂离子电池浆料的制备方法, 其特征在于, 包括以下步骤:
S10、 将活性材料、 粘结剂和导电剂除铁后与溶剂一起投入双轴桨叶 式高效混合机中, 混合均匀, 形成预混浆料;
S20、 将所述预混浆料搅拌以混合均匀, 形成混合浆料;
S30、 将所述混合浆料投入高速分散机中进行高速分散, 形成固含量 为 70-80%的半成品浆料;
S40、 将所述半成品浆料真空下除泡, 过筛, 形成锂离子电池浆料。
[权利要求 3] 根据权利要求 1或 2所述的制备方法, 其特征在于, 步骤 S10中, 混合 吋间为 3-5分钟。
[权利要求 4] 根据权利要求 1或 2所述的制备方法, 其特征在于, 步骤 S10中, 所述 活性材料、 粘结剂及导电剂通过除铁器进行除铁, 除铁吋间≤30分钟
[权利要求 5] 根据权利要求 1或 2所述的制备方法, 其特征在于, 步骤 S20的混合浆 料在搅拌机中混合形成, 所述搅拌机公转速度≤15r/min, 自转速度≤1
OOOr/min, 搅拌混合吋间≤60分钟。
[权利要求 6] 根据权利要求 1或 2所述的制备方法, 其特征在于, 步骤 S30中, 高速 分散的线速度为 66m/s, 分散过程中控制浆料温度为 20~45°C。
[权利要求 7] 根据权利要求 1或 2所述的制备方法, 其特征在于, 步骤 S40中, 真空 下除泡吋间为 10-30分钟, 真空度≥-0.08Mpa。
[权利要求 8] 根据权利要求 1或 2所述的制备方法, 其特征在于, 所述活性材料为正 极活性材料或负极活性材料, 所述溶剂为 N-甲基吡咯烷酮或去离子水
[权利要求 9] 根据权利要求 8所述的制备方法, 其特征在于, 所述正极活性材料为 锂钴氧化物 (LiCo0 2) 、 锂镍氧化物 (LiNi0 2
) 、 锂锰氧化物 (LiMn 20 4) 、 锰镍钴复合氧化物 (LiMn xNi yCo yO 2) 、 锂钒氧化物 (LiV 20 4) 或锂铁氧化物 (LiFePO 2) 中的一 种或多种; 所述负极活性材料为人造石墨、 天然石墨或中间相碳微球 中的一种或多种, 其中, x、 y、 x+y均大于 0小于 1 ;
所述粘结剂为聚乙烯醇、 聚偏氟乙烯、 偏二氟乙烯、 聚四氟乙烯、 六 氟丙烯、 丙烯酸酯、 聚氨酯、 羧甲基纤维素钠中的一种或多种; 所述 导电剂为导电炭黑、 导电石墨、 碳纤维、 碳纳米管中的一种或多种。
[权利要求 10] 一种锂离子电池浆料, 其特征在于, 采用权利要求 1-9任一项所述的 制备方法制得。
PCT/CN2017/113399 2016-12-22 2017-11-28 锂离子电池浆料及其制备方法 Ceased WO2018113486A1 (zh)

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