WO2016202168A1 - Lithium-ion battery positive-electrode slurry and preparation method therefor - Google Patents

Lithium-ion battery positive-electrode slurry and preparation method therefor Download PDF

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WO2016202168A1
WO2016202168A1 PCT/CN2016/083962 CN2016083962W WO2016202168A1 WO 2016202168 A1 WO2016202168 A1 WO 2016202168A1 CN 2016083962 W CN2016083962 W CN 2016083962W WO 2016202168 A1 WO2016202168 A1 WO 2016202168A1
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positive electrode
ion battery
lithium ion
added
electrode slurry
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田东
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田东
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the patent relates to a lithium ion battery positive electrode slurry and a preparation method thereof, in particular to the application of carbon nanotubes and carbon fiber materials in a positive electrode of a lithium ion battery.
  • Lithium-ion batteries have the advantages of high energy density, small self-discharge, no memory effect, wide operating voltage range, long service life and no environmental pollution. They are the main power source for new energy vehicles.
  • the key electrode material of lithium ion battery is the final determinant of battery performance, and the positive electrode material plays an important role in improving the performance of lithium ion battery. Therefore, the development of high-performance, low-cost cathode materials is of great significance to promote the development of new energy vehicles and related emerging industries.
  • the positive electrode material of a lithium ion battery is generally an excessive metal oxide such as LiCoO 2 , LiNiO 2 , LiMnO 2 , and LiNi x Co y Mn (1-xy) O 2 , and a phosphate of an excessive metal such as LiMPO 4 . They have low electrical conductivity and are generally semiconductor or insulator.
  • the ideal positive electrode is a mixed conductor of ions and electrons.
  • the electronic conductivity is related to the conductivity of the positive electrode.
  • the ion conductivity is related to the pore volume of the positive electrode.
  • the porous structure can provide a storage place for the electrolyte and provide a buffer ion source for the rapid reaction of the electrode. .
  • the role of the conductive agent in the positive electrode is mainly to improve the conductivity of the positive electrode.
  • Excellent conductive agent needs to have the following characteristics: First, the conductivity is high, the material with high conductivity can increase the migration rate of electrons; Second, the particle size is small, the material with small particle size can fill the positive and negative electrodes of lithium ion battery. The voids of the material make the contact between the materials better, and the lithium ions are easily released and embedded. Third, the material with high specific surface area and large specific surface area can be better contacted with the positive and positive materials, and is also easy to maintain the electrolyte. It facilitates the deintercalation and electron transfer of lithium ions; 4. It is easy to disperse, easy to disperse and disperse in the process of slurry preparation of positive and positive materials, and can be better mixed with positive and positive materials; 5. High stability, In the process of charging and discharging a lithium ion battery, it can be stably existed without a volume change and affecting the cycle performance of the battery.
  • the conductive agents for lithium-ion batteries are mainly Super-P and KS series. Both of these products are imported from abroad.
  • the former is a nano-scale carbon black product, which has a small particle size and a large specific surface area. It also has good electrical conductivity, but because of its small particle size and large specific surface area, it is difficult to disperse, and then it is micron-sized conductive graphite, which is easy to disperse, but its conductivity is worse than Super-P. Therefore, in the actual use process, both are added at the same time, and the complement is insufficient.
  • Carbon nanotubes and carbon fibers have the characteristics of high strength, excellent electrical conductivity, and good thermal conductivity. Because of their long fibrous structure, both of them are added to the positive electrode at the same time, and can be entangled with the components of the positive electrode material to strengthen the positive electrode. The combination of materials and electrical conductivity enhances the capacity and cycle performance of the battery.
  • the purpose of this patent is to provide a lithium ion battery positive electrode slurry and a preparation method thereof to improve battery capacity and improve battery cycle life.
  • a lithium ion battery positive electrode slurry comprising a positive electrode active material, a conductive agent, a binder, a solvent and a dispersing agent, characterized in that it further comprises carbon nanotubes and carbon fibers.
  • the conductive agent accounts for 0%-3% of the total solid weight
  • the dispersant is added in an amount of 0%-5% of the total solid mass fraction
  • the carbon nanotubes account for 1%-3% of the total solids
  • the carbon fiber accounts for the total solid weight.
  • 1% to 5% of the carbon fiber has a straight particle diameter D50 of between 10 and 200 nm.
  • the carbon fiber is a hollow or solid structure.
  • the hollow structure of the carbon fiber is a single layer hollow or a plurality of layers hollow.
  • the positive electrode active material is a mixture of one or more of LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiNi x Co y Mn (1-xy) O 2 and LiFePO 4 .
  • the conductive agent is one of Super-P, graphite conductive agent, and Ketjen black.
  • the binder is polyvinylidene fluoride.
  • the dispersing agent is ethylene glycol or glycerol.
  • a preparation step of a lithium ion battery positive electrode slurry is a preparation step of a lithium ion battery positive electrode slurry.
  • the binder polyvinylidene fluoride is uniformly dissolved by a stirrer; then, super-P is added, and the mixture is dispersed by a ball mill for 1 hour; the positive electrode active material is added, and the ball mill is dispersed for 2 hours;
  • This patent uses ball milling method and uses dispersant to add carbon nanotubes and carbon fibers to the positive electrode of lithium ion battery in proportion, using carbon nanotubes and carbon fiber. It has high strength, excellent electrical conductivity, good thermal conductivity, and its fibrous structure, which is entangled with components such as a positive electrode active material and a conductive agent to strengthen the positive electrode material and increase conductivity. Thereby increasing battery capacity and improving battery cycle life.
  • carbon nanotubes and carbon fibers are added according to the ratio and the method of furnishing provided in this patent during the positive electrode batching, and the capacity and cycle performance of the lithium ion battery are improved.
  • the length of the positive and negative electrode sheets was calculated according to the steel shell filling rate of 95%, and the examples and comparative examples are positive electrode batching methods and ratio examples.
  • the binder polyvinylidene fluoride having a solid mass fraction of 1.5% was dissolved uniformly with a stirrer using N-methylpyrrolidone as a solvent. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
  • Lithium cobaltate having a solid mass fraction of 92.5% was added and dispersed by a ball mill for 2 hours.
  • the dispersant ethylene glycol was added in an amount of 2% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 3% and carbon fibers having a mass fraction of 3% were added to the mixed liquid for further one hour.
  • the binder polyvinylidene fluoride having a solid mass fraction of 1.5% was dissolved uniformly with a stirrer using N-methylpyrrolidone as a solvent. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
  • Lithium cobaltate having a solid mass fraction of 92.5% was added and dispersed by a ball mill for 2 hours.
  • the dispersant ethylene glycol which accounts for 2% of the solid mass fraction, was added and dispersion continued for 1 hour.
  • the binder polyvinylidene fluoride having a solid mass fraction of 1.5% was dissolved uniformly with a stirrer using N-methylpyrrolidone as a solvent. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
  • Lithium manganate which accounts for 93% of the solid mass fraction, was added and dispersed by a ball mill for 2 hours.
  • the dispersant ethylene glycol was added in an amount of 1% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 2% and carbon powder having a mass fraction of 2.5% were added to the mixed liquid for further one hour.
  • the binder polyvinylidene fluoride having a solid mass fraction of 1.5% was dissolved uniformly with a stirrer using N-methylpyrrolidone as a solvent. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
  • Lithium manganate which accounts for 93% of the solid mass fraction, was added and dispersed by a ball mill for 2 hours.
  • the dispersant ethylene glycol was added in an amount of 1% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 2% and carbon powder having a mass fraction of 2.5% were added to the mixed liquid for further one hour.
  • a binder polyvinylidene fluoride having a solid mass fraction of 2% was dissolved uniformly with a stirrer. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
  • Lithium iron phosphate which accounts for 94% of the solid mass fraction, was added and dispersed by a ball mill for 2 hours.
  • the dispersant ethylene glycol was added in an amount of 1% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 1.5% and carbon fibers having a mass fraction of 1.5% were added to the mixed liquid for further one hour.
  • a binder polyvinylidene fluoride having a solid mass fraction of 2% was dissolved uniformly with a stirrer. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
  • Lithium iron phosphate which accounts for 94% of the solid mass fraction, was added and dispersed by a ball mill for 2 hours.
  • the dispersant ethylene glycol was added in an amount of 1% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 1.5% and carbon fibers having a mass fraction of 1.5% were added to the mixed liquid for further one hour.
  • the positive electrode sheets of lithium ion batteries were prepared from the pastes prepared by the methods of the comparative examples and the examples, and the batteries were assembled.
  • the data of the internal resistance, capacity, first efficiency, and 300-cycle capacity retention of the batteries are shown in Table 1.

Abstract

A lithium-ion battery positive-electrode slurry and a preparation method therefor. The lithium-ion battery positive-electrode slurry comprises a positive-electrode active material, a conductive agent, a binder, a solvent and a dispersant, and is characterized by further comprising carbon nanotubes and carbon fibers. According to the present invention, carbon nanotubes and carbon fibers are added to the positive electrode of a lithium-ion battery in proportion. As carbon nanotubes and carbon fibers have high strength, excellent conductivity, good thermal conductivity, and a fibroid structure, wrapping of carbon fibers with such ingredients as the positive-electrode active material and the conductive agent can provide an effect of reinforcing the positive-electrode material and increasing the conductivity, thereby improving the battery capacity and prolonging the cycle life of the battery.

Description

一种锂离子电池正极浆料及其制备方法Lithium ion battery positive electrode slurry and preparation method thereof 技术领域Technical field
本专利涉及一种锂离子电池正极浆料及其制备方法，具体为碳纳米管和碳纤维材料在锂离子电池正极中的应用。The patent relates to a lithium ion battery positive electrode slurry and a preparation method thereof, in particular to the application of carbon nanotubes and carbon fiber materials in a positive electrode of a lithium ion battery.
背景技术Background technique
目前随着全球性石油资源紧缺与气候环境的不断恶化，人类社会发展面临着严峻的挑战。发展清洁节能的新能源汽车受到世界各国的高度重视。新能源汽车的发展，关键在其动力电源。锂离子电池具有能量密度大、自放电小、无记忆效应、工作电压范围宽、使用寿命长、无环境污染等优点，是目前新能源汽车主要的动力电源。而锂离子电池关键电极材料是电池性能的最终决定性因素，其中正极材料对锂离子电池性能的提高起着至关重要的作用。因此，开发高性能、廉价的正极材料对促进新能源汽车及相关新兴产业的发展具有重要的意义。At present, with the shortage of global petroleum resources and the deteriorating climate environment, the development of human society faces severe challenges. The development of clean and energy-efficient new energy vehicles has been highly valued by countries around the world. The development of new energy vehicles is the key to their power supply. Lithium-ion batteries have the advantages of high energy density, small self-discharge, no memory effect, wide operating voltage range, long service life and no environmental pollution. They are the main power source for new energy vehicles. The key electrode material of lithium ion battery is the final determinant of battery performance, and the positive electrode material plays an important role in improving the performance of lithium ion battery. Therefore, the development of high-performance, low-cost cathode materials is of great significance to promote the development of new energy vehicles and related emerging industries.
锂离子电池的正极材料一般为过度金属氧化物，如：LiCoO2、LiNiO2、LiMnO2、和LiNixCoyMn(1-x-y)O2等，以及过度金属的磷酸盐，如：LiMPO4；它们电导率低，一般是半导体或是绝缘体。理想的正极为离子和电子的混合导体，电子导电性和正极导电性好坏有关；离子传导性和正极的孔容有关，多孔结构可以提供电解液的存储场所，为电极快速反应提供缓冲离子源。导电剂在正极的作用主要是提高正极的导电性。 The positive electrode material of a lithium ion battery is generally an excessive metal oxide such as LiCoO 2 , LiNiO 2 , LiMnO 2 , and LiNi x Co y Mn (1-xy) O 2 , and a phosphate of an excessive metal such as LiMPO 4 . They have low electrical conductivity and are generally semiconductor or insulator. The ideal positive electrode is a mixed conductor of ions and electrons. The electronic conductivity is related to the conductivity of the positive electrode. The ion conductivity is related to the pore volume of the positive electrode. The porous structure can provide a storage place for the electrolyte and provide a buffer ion source for the rapid reaction of the electrode. . The role of the conductive agent in the positive electrode is mainly to improve the conductivity of the positive electrode.
优异的导电剂需要具备以下几个特征：一、电导率较高，高电导率的材料能提高电子的迁移速率；二、粒径较小，小粒径的材料能填充锂离子电池正、正极材料的空隙，使材料之间的接触较好，易于锂离子的脱出、嵌入；三、高比表面积，比表面积大的材料能较好的与正、正极材料接触，同样易于电解液的保持，便于锂离子的脱嵌与电子迁移；四、易于分散，在正、正极材料配置浆料过程中易于打散和分散，能较好的与正、正极材料混合在一起；五、高稳定性，在锂离子电池充放电的过程中能稳定存在，不会发生体积变化而影响电池的循环性能。Excellent conductive agent needs to have the following characteristics: First, the conductivity is high, the material with high conductivity can increase the migration rate of electrons; Second, the particle size is small, the material with small particle size can fill the positive and negative electrodes of lithium ion battery. The voids of the material make the contact between the materials better, and the lithium ions are easily released and embedded. Third, the material with high specific surface area and large specific surface area can be better contacted with the positive and positive materials, and is also easy to maintain the electrolyte. It facilitates the deintercalation and electron transfer of lithium ions; 4. It is easy to disperse, easy to disperse and disperse in the process of slurry preparation of positive and positive materials, and can be better mixed with positive and positive materials; 5. High stability, In the process of charging and discharging a lithium ion battery, it can be stably existed without a volume change and affecting the cycle performance of the battery.
目前市场上锂离子电池导电剂主要为Super-P与KS系列，此两类产品皆为国外进口，前者为纳米级的炭黑类产品，既有较小的粒径和较大的比表面积，又具有较好的导电性能，但是由于粒径较小及比表面积较大，不易分散，而后则为微米级的导电石墨，易于分散，但是导电性能较Super-P差。所以实际使用过程中，两者都是同时添加使用，互补不足。At present, the conductive agents for lithium-ion batteries are mainly Super-P and KS series. Both of these products are imported from abroad. The former is a nano-scale carbon black product, which has a small particle size and a large specific surface area. It also has good electrical conductivity, but because of its small particle size and large specific surface area, it is difficult to disperse, and then it is micron-sized conductive graphite, which is easy to disperse, but its conductivity is worse than Super-P. Therefore, in the actual use process, both are added at the same time, and the complement is insufficient.
碳纳米管与碳纤维具有强度高、导电性优良、导热性良好等特点，由于其具有纤长的纤维状结构，两者同时添加到正极中，可与正极材料各组份相互缠绕，起到加固正极材料、增加导电性的作用，两者协同配合，提高了电池的容量和循环性能。Carbon nanotubes and carbon fibers have the characteristics of high strength, excellent electrical conductivity, and good thermal conductivity. Because of their long fibrous structure, both of them are added to the positive electrode at the same time, and can be entangled with the components of the positive electrode material to strengthen the positive electrode. The combination of materials and electrical conductivity enhances the capacity and cycle performance of the battery.
发明内容Summary of the invention
本专利的目的是提供一种锂离子电池正极浆料及其制备方法，以提高电池容量、改善电池循环寿命。 The purpose of this patent is to provide a lithium ion battery positive electrode slurry and a preparation method thereof to improve battery capacity and improve battery cycle life.
为实现上述目的，本专利采用的技术方案是：一种锂离子电池正极浆料，包括正极活性物质、导电剂、粘结剂、溶剂和分散剂，其特征是，还包括碳纳米管和碳纤维，导电剂占总固体重量的0％-3％，分散剂加入量占总固体质量分数的0％-5％，碳纳米管占总固体量的1％-3％，碳纤维占总固体量重量的1％-5％，所述碳纤维中直粒径径D50介于10-200nm之间。In order to achieve the above object, the technical solution adopted in this patent is: a lithium ion battery positive electrode slurry, comprising a positive electrode active material, a conductive agent, a binder, a solvent and a dispersing agent, characterized in that it further comprises carbon nanotubes and carbon fibers. The conductive agent accounts for 0%-3% of the total solid weight, the dispersant is added in an amount of 0%-5% of the total solid mass fraction, the carbon nanotubes account for 1%-3% of the total solids, and the carbon fiber accounts for the total solid weight. 1% to 5% of the carbon fiber has a straight particle diameter D50 of between 10 and 200 nm.
所述碳纤维为中空或实心结构。The carbon fiber is a hollow or solid structure.
所述碳纤维的中空结构为单层中空或多层中空。The hollow structure of the carbon fiber is a single layer hollow or a plurality of layers hollow.
所述正极活性物质为LiCoO2、LiNiO2、LiMn2O4、LiNixCoyMn(1-x-y)O2和LiFePO4中的一种或多种混合物。The positive electrode active material is a mixture of one or more of LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiNi x Co y Mn (1-xy) O 2 and LiFePO 4 .
导电剂为Super-P、石墨导电剂、科琴黑中的一种。The conductive agent is one of Super-P, graphite conductive agent, and Ketjen black.
所述溶剂为N-甲基吡咯烷酮时，粘结剂为聚偏氟乙烯。When the solvent is N-methylpyrrolidone, the binder is polyvinylidene fluoride.
所述分散剂为乙二醇或丙三醇。The dispersing agent is ethylene glycol or glycerol.
一种锂离子电池正极浆料的制备步骤：A preparation step of a lithium ion battery positive electrode slurry:
(1)以N-甲基吡咯烷酮为溶剂，将粘结剂聚偏氟乙烯用搅拌机溶解均匀；然后加入super-P，球磨分散1小时；加入正极活性物质，球磨分散2小时；(1) using N-methylpyrrolidone as a solvent, the binder polyvinylidene fluoride is uniformly dissolved by a stirrer; then, super-P is added, and the mixture is dispersed by a ball mill for 1 hour; the positive electrode active material is added, and the ball mill is dispersed for 2 hours;
(2)加入分散剂，球磨分散10分钟后将碳纳米管和碳纤维加入混合液体中继续分散1小时；(2) adding a dispersing agent, after the ball mill is dispersed for 10 minutes, the carbon nanotubes and carbon fibers are added to the mixed liquid to continue to disperse for 1 hour;
(3)调节浆料粘度到至3000-4000mPa·s，出料。(3) Adjust the viscosity of the slurry to 3000-4000 mPa·s, and discharge.
本专利运用球磨方式配料，并配合使用分散剂，将碳纳米管和碳纤维按比例添加到锂离子电池正极之中，利用碳纳米管和碳纤维 具有强度高、导电性优良、导热性良好，以及其具有的纤维状结构特点，使其与正极活性物质、导电剂等各组份相互缠绕，起到加固正极材料、增加导电性的作用。从而提高电池容量、改善电池循环寿命。This patent uses ball milling method and uses dispersant to add carbon nanotubes and carbon fibers to the positive electrode of lithium ion battery in proportion, using carbon nanotubes and carbon fiber. It has high strength, excellent electrical conductivity, good thermal conductivity, and its fibrous structure, which is entangled with components such as a positive electrode active material and a conductive agent to strengthen the positive electrode material and increase conductivity. Thereby increasing battery capacity and improving battery cycle life.
具体实施方式detailed description
以圆柱型18650锂离子电池为例，在正极配料时按本专利所提供的比例及配料方法添加碳纳米管和碳纤维，对比说明其对锂离子电池容量及循环性能改善。电池设计中，按钢壳填充率95％计算正负极片长度，实施例与比较例为正极配料方式及配比举例。Taking a cylindrical 18650 lithium ion battery as an example, carbon nanotubes and carbon fibers are added according to the ratio and the method of furnishing provided in this patent during the positive electrode batching, and the capacity and cycle performance of the lithium ion battery are improved. In the battery design, the length of the positive and negative electrode sheets was calculated according to the steel shell filling rate of 95%, and the examples and comparative examples are positive electrode batching methods and ratio examples.
实施例1Example 1
以N-甲基吡咯烷酮为溶剂，将占固体质量分数为1.5％的粘结剂聚偏氟乙烯用搅拌机溶解均匀。然后加入占固体质量分数1％的super-P，球磨分散1小时。The binder polyvinylidene fluoride having a solid mass fraction of 1.5% was dissolved uniformly with a stirrer using N-methylpyrrolidone as a solvent. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
加入占固体质量分数92.5％的钴酸锂，球磨分散2小时。Lithium cobaltate having a solid mass fraction of 92.5% was added and dispersed by a ball mill for 2 hours.
加入占固体质量分数2％的分散剂乙二醇，球磨分散10分钟后将占固体质量分数3％的碳纳米管和占质量分数3％碳纤维加入混合液体中继续分散1小时。The dispersant ethylene glycol was added in an amount of 2% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 3% and carbon fibers having a mass fraction of 3% were added to the mixed liquid for further one hour.
调节浆料粘度到合理范围，出料。Adjust the viscosity of the slurry to a reasonable range and discharge.
比较例1Comparative example 1
以N-甲基吡咯烷酮为溶剂，将占固体质量分数为1.5％的粘结剂聚偏氟乙烯用搅拌机溶解均匀。然后加入占固体质量分数1％的super-P，球磨分散1小时。The binder polyvinylidene fluoride having a solid mass fraction of 1.5% was dissolved uniformly with a stirrer using N-methylpyrrolidone as a solvent. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
加入占固体质量分数92.5％的钴酸锂，球磨分散2小时。 Lithium cobaltate having a solid mass fraction of 92.5% was added and dispersed by a ball mill for 2 hours.
加入占固体质量分数2％的分散剂乙二醇，继续分散1小时。The dispersant ethylene glycol, which accounts for 2% of the solid mass fraction, was added and dispersion continued for 1 hour.
调节浆料粘度到合理范围，出料。Adjust the viscosity of the slurry to a reasonable range and discharge.
实施例2Example 2
以N-甲基吡咯烷酮为溶剂，将占固体质量分数为1.5％的粘结剂聚偏氟乙烯用搅拌机溶解均匀。然后加入占固体质量分数1％的super-P，球磨分散1小时。The binder polyvinylidene fluoride having a solid mass fraction of 1.5% was dissolved uniformly with a stirrer using N-methylpyrrolidone as a solvent. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
加入占固体质量分数93％的锰酸锂，球磨分散2小时。Lithium manganate, which accounts for 93% of the solid mass fraction, was added and dispersed by a ball mill for 2 hours.
加入占固体质量分数1％的分散剂乙二醇，球磨分散10分钟后将占固体质量分数2％的碳纳米管和占质量分数2.5％碳纤维加入混合液体中继续分散1小时。The dispersant ethylene glycol was added in an amount of 1% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 2% and carbon powder having a mass fraction of 2.5% were added to the mixed liquid for further one hour.
调节浆料粘度到合理范围，出料。Adjust the viscosity of the slurry to a reasonable range and discharge.
比较例2Comparative example 2
以N-甲基吡咯烷酮为溶剂，将占固体质量分数为1.5％的粘结剂聚偏氟乙烯用搅拌机溶解均匀。然后加入占固体质量分数1％的super-P，球磨分散1小时。The binder polyvinylidene fluoride having a solid mass fraction of 1.5% was dissolved uniformly with a stirrer using N-methylpyrrolidone as a solvent. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
加入占固体质量分数93％的锰酸锂，球磨分散2小时。Lithium manganate, which accounts for 93% of the solid mass fraction, was added and dispersed by a ball mill for 2 hours.
加入占固体质量分数1％的分散剂乙二醇，球磨分散10分钟后将占固体质量分数2％的碳纳米管和占质量分数2.5％碳纤维加入混合液体中继续分散1小时。The dispersant ethylene glycol was added in an amount of 1% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 2% and carbon powder having a mass fraction of 2.5% were added to the mixed liquid for further one hour.
调节浆料粘度到合理范围，出料。Adjust the viscosity of the slurry to a reasonable range and discharge.
实施例3 Example 3
以N-甲基吡咯烷酮为溶剂，将占固体质量分数为2％的粘结剂聚偏氟乙烯用搅拌机溶解均匀。然后加入占固体质量分数1％的super-P，球磨分散1小时。Using N-methylpyrrolidone as a solvent, a binder polyvinylidene fluoride having a solid mass fraction of 2% was dissolved uniformly with a stirrer. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
加入占固体质量分数94％的磷酸铁锂，球磨分散2小时。Lithium iron phosphate, which accounts for 94% of the solid mass fraction, was added and dispersed by a ball mill for 2 hours.
加入占固体质量分数1％的分散剂乙二醇，球磨分散10分钟后将占固体质量分数1.5％的碳纳米管和占质量分数1.5％碳纤维加入混合液体中继续分散1小时。The dispersant ethylene glycol was added in an amount of 1% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 1.5% and carbon fibers having a mass fraction of 1.5% were added to the mixed liquid for further one hour.
调节浆料粘度到合理范围，出料。Adjust the viscosity of the slurry to a reasonable range and discharge.
对比例3Comparative example 3
以N-甲基吡咯烷酮为溶剂，将占固体质量分数为2％的粘结剂聚偏氟乙烯用搅拌机溶解均匀。然后加入占固体质量分数1％的super-P，球磨分散1小时。Using N-methylpyrrolidone as a solvent, a binder polyvinylidene fluoride having a solid mass fraction of 2% was dissolved uniformly with a stirrer. Then, super-P, which accounts for 1% of the solid mass fraction, was added and the ball mill was dispersed for 1 hour.
加入占固体质量分数94％的磷酸铁锂，球磨分散2小时。Lithium iron phosphate, which accounts for 94% of the solid mass fraction, was added and dispersed by a ball mill for 2 hours.
加入占固体质量分数1％的分散剂乙二醇，球磨分散10分钟后将占固体质量分数1.5％的碳纳米管和占质量分数1.5％碳纤维加入混合液体中继续分散1小时。The dispersant ethylene glycol was added in an amount of 1% by mass of the solid, and after dispersing for 10 minutes by ball milling, carbon nanotubes having a solid mass fraction of 1.5% and carbon fibers having a mass fraction of 1.5% were added to the mixed liquid for further one hour.
调节浆料粘度到合理范围，出料。Adjust the viscosity of the slurry to a reasonable range and discharge.
由比较例和实施例方法制备的浆料制作锂离子电池正极片，并装配电池，其电池内阻、容量、首次效率和300周循环容量保持率的数据列于表1。 The positive electrode sheets of lithium ion batteries were prepared from the pastes prepared by the methods of the comparative examples and the examples, and the batteries were assembled. The data of the internal resistance, capacity, first efficiency, and 300-cycle capacity retention of the batteries are shown in Table 1.
表1Table 1
Figure PCTCN2016083962-appb-000001
Figure PCTCN2016083962-appb-000001
对比实施例1和比较例1、实施例2和比较例2、实施例3和比较例3可发现，在正极中添加碳纳米管和碳纤维可有效降低电池的内阻、提高电池容量以及循环性能。原因在于碳纳米管和碳纤维具有的纤维状结构特点，使其与正极活性物质、导电剂等各组份相互缠绕，起到加固正极材料、增加导电性的作用，从而提高了电池容量、改善了电池的循环寿命。 Comparing Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, it was found that the addition of carbon nanotubes and carbon fibers to the positive electrode can effectively reduce the internal resistance of the battery, improve the battery capacity and cycle performance. . The reason is that the carbon nanotubes and carbon fibers have the fibrous structural characteristics, which are intertwined with the positive electrode active material and the conductive agent, thereby reinforcing the positive electrode material and increasing the conductivity, thereby improving the battery capacity and improving the battery capacity. The cycle life of the battery.

Claims (7)

  1. 一种锂离子电池正极浆料及其制备方法，包括正极活性物质、导电剂、粘结剂、溶剂和分散剂，其特征是，还包括碳纳米管和碳纤维，导电剂占总固体重量的0％-3％，分散剂加入量占总固体质量分数的0％-5％，碳纳米管占总固体量的1％-3％，碳纤维占总固体量重量的1％-5％，所述碳纤维中直粒径径D50介于10-200nm之间，其制备步骤如下：A lithium ion battery positive electrode slurry and a preparation method thereof, comprising a positive electrode active material, a conductive agent, a binder, a solvent and a dispersing agent, characterized in that the carbon nanotube and the carbon fiber are further included, and the conductive agent accounts for 0 of the total solid weight. %-3%, the dispersant is added in an amount of 0% to 5% of the total solid mass fraction, the carbon nanotubes are 1% to 3% of the total solids, and the carbon fibers are 1% to 5% by weight of the total solids. The straight fiber diameter D50 of the carbon fiber is between 10 and 200 nm, and the preparation steps are as follows:
    (1)将粘结剂聚加入溶剂用搅拌机溶解均匀，然后加入导电剂，球磨分散1小时，再加入正极活性物质，球磨分散2小时；(1) The binder is polymerized into a solvent and dissolved uniformly by a stirrer, then a conductive agent is added, and the ball is dispersed for 1 hour, and then the positive electrode active material is added, and the ball mill is dispersed for 2 hours;
    (2)加入分散剂，球磨分散10分钟后将碳纳米管和碳纤维加入混合液体中继续分散1小时；(2) adding a dispersing agent, after the ball mill is dispersed for 10 minutes, the carbon nanotubes and carbon fibers are added to the mixed liquid to continue to disperse for 1 hour;
    (3)调节浆料粘度到至3000-4000mPa·s，出料。(3) Adjust the viscosity of the slurry to 3000-4000 mPa·s, and discharge.
  2. 根据权利要求1所述的一种锂离子电池正极浆料及其制备方法，其特征是，所述碳纤维为中空或实心结构。A positive electrode slurry for a lithium ion battery according to claim 1 or a method for producing the same, characterized in that the carbon fiber is a hollow or solid structure.
  3. 根据权利要求2所述的一种锂离子电池正极浆料及其制备方法，其特征是，所述碳纤维的中空结构为单层中空或多层中空。The lithium ion battery positive electrode slurry and the preparation method thereof according to claim 2, wherein the carbon fiber has a hollow structure of a single layer of hollow or a plurality of layers of hollow.
  4. 根据权利要求1所述的一种锂离子电池正极浆料及其制备方法，其特征是，所述正极活性物质为LiCoO2、LiNiO2、LiMn2O4、LiNixCoyMn(1-x-y)O2和LiFePO4中的一种或多种混合物。A positive electrode slurry for a lithium ion battery according to claim 1 or a method for producing the same, characterized in that the positive electrode active material is LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiNi x Co y Mn (1-xy ) one of the LiFePO 4 O 2 or more and mixtures thereof.
  5. 根据权利要求1所述的一种锂离子电池正极浆料及其制备方法，其特征是，所述，导电剂为Super-P、石墨导电剂、科琴黑中的一种。The lithium ion battery positive electrode slurry according to claim 1 and the method for preparing the same, wherein the conductive agent is one of Super-P, graphite conductive agent and Ketjen black.
  6. 根据权利要求1所述的一种锂离子电池正极浆料及其制备方法，其特征是，所述溶剂为N-甲基吡咯烷酮，粘结剂为聚偏氟乙烯。 The positive electrode slurry for lithium ion battery according to claim 1 and the method for preparing the same, wherein the solvent is N-methylpyrrolidone and the binder is polyvinylidene fluoride.
  7. 根据权利要求1所述的一种锂离子电池正极浆料及其制备方法，其特征是，所述分散剂为乙二醇或丙三醇。 A positive electrode slurry for a lithium ion battery according to claim 1 or a method for producing the same, characterized in that the dispersing agent is ethylene glycol or glycerin.
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