WO2017032167A1 - Preparation method for lithium cobalt oxide positive-electrode slurry - Google Patents

Preparation method for lithium cobalt oxide positive-electrode slurry Download PDF

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WO2017032167A1
WO2017032167A1 PCT/CN2016/087184 CN2016087184W WO2017032167A1 WO 2017032167 A1 WO2017032167 A1 WO 2017032167A1 CN 2016087184 W CN2016087184 W CN 2016087184W WO 2017032167 A1 WO2017032167 A1 WO 2017032167A1
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slurry
viscosity
positive electrode
minutes
stirring
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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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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 the field of lithium ion batteries, in particular to a preparation process and a method for a lithium cobaltate cathode material slurry.
  • 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.
  • a lithium ion battery generally includes a positive electrode sheet, a negative electrode sheet, and a separator interposed between the positive electrode sheet and the negative electrode sheet.
  • the positive electrode tab includes a positive electrode current collector and a positive electrode film coated on the positive electrode current collector
  • the negative electrode plate includes a negative electrode current collector and a negative electrode film coated on the negative electrode current collector.
  • an active material such as lithium cobaltate, graphite, etc.
  • a conductive agent such as acetylene black, carbon nanotubes, carbon fiber, etc.
  • a binder such as polyvinylidene fluoride, polyvinylpyrrolidone, Carboxymethylcellulose sodium, styrene-butadiene rubber emulsion, etc.
  • a solvent such as N-methylpyrrolidone, water, etc.
  • the performance of the electrode paste has an important influence on the performance of the lithium ion battery.
  • the effect of the active substance can be exerted during charging and discharging, and the average gram capacity is exerted. Will be improved to improve the performance of the full battery.
  • the conventional positive electrode slurry preparation method is to carry out high-speed double planetary dispersion of a conductive agent with a binder solution, and then add a positive electrode active material, and stir for a certain period of time to obtain a final positive electrode slurry.
  • This method firstly requires a long time treatment for the dispersion of the conductive agent, which takes a long time and is not ideal in the dispersion state, especially for the preparation of a slurry using a carbon nanotube (CNT), graphene or the like as a conductive agent; the second conventional process needs to be During the preparation of the slurry, the stirring system is kept under vacuum, which causes the internal temperature of the slurry system to rise easily, and at the same time, externally added circulating water for cooling, so the requirements and wear of the equipment are high.
  • the above results in low slurry preparation efficiency, poor stability, and unsatisfactory effect, which will affect the preparation of the subsequent pole piece and the performance of the lithium battery.
  • an object of the present invention is to provide a method for preparing a lithium battery lithium cobaltate positive electrode slurry, which is capable of uniformly dispersing the components of the slurry in a relatively short time, and preparing the same.
  • the slurry has good uniformity and excellent stability, and at the same time, the prepared battery sheet adhesion is improved, and thus the consistency of the battery and the electrochemical performance of the battery are improved.
  • Disperse powder Add lithium cobalt oxide, conductive agent and binder to the mixing tank in proportion and stir for 30 to 40 minutes. At time 1/2 and at the end, scrape the paddle and the barrel. Powder
  • High-viscosity stirring adding 55% to 60% of the total amount of the solvent to the stirred powder, stirring and dispersing for 60 to 70 minutes, and scraping at time 1/3, 2/3 and at the end Stir the slurry on the paddle and the barrel, and the slurry temperature is controlled between 25 and 35 ° C;
  • Low-viscosity stirring adding 35 to 30% of the total amount of the solvent to the above-mentioned high-viscosity stirred slurry, stirring and dispersing for 60 to 70 minutes, and at the time of 1/3, 2/3 and at the end, Scrape the paddle and the slurry on the barrel, and the slurry temperature is controlled between 25 and 35 ° C;
  • Viscosity test the viscosity of the slurry with low viscosity stirring in the above steps is tested for viscosity, such as in the normal range of 4000-7000 Mpa ⁇ S, directly into the next vacuum defoaming; if it exceeds the above range, 5% of the total amount of solvent is added. ⁇ 10%, stir and disperse for a period of 30 to 40 minutes, and at time 1/2 and at the end, scrape the slurry on the paddle and the barrel, and then test the viscosity of the slurry to reach the viscosity range.
  • Next step the viscosity of the slurry with low viscosity stirring in the above steps is tested for viscosity, such as in the normal range of 4000-7000 Mpa ⁇ S, directly into the next vacuum defoaming; if it exceeds the above range, 5% of the total amount of solvent is added. ⁇ 10%, stir and disperse for a period of 30 to 40 minutes, and at time 1/2 and at the end,
  • Vacuum defoaming Under low-speed stirring, the barrel is evacuated, the degree of vacuum is -0.09 to -0.1 MPa, and the time is 15 to 30 minutes, that is, the positive electrode slurry prepared by the method of the invention is obtained.
  • the conductive agent in the above step 1 is one or a mixture of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers, and graphene.
  • the binder in the above step 1 is polyvinylidene fluoride (PVDF).
  • the solvent in the above step 2 is N-methylpyrrolidone (NMP).
  • the mass ratio of each component of the lithium cobaltate, the conductive agent, and the binder is (90-97): (1-4): (1-5), and the solvent is the above components. 60% to 90% of the total weight.
  • the agitation device is a dual planetary vacuum agitator, and the slurry temperature is controlled by a method of introducing a constant temperature circulating water to the planetary agitating barrel at a corresponding temperature.
  • the present invention has the following advantages:
  • the preparation time of the positive electrode slurry of the invention is about 195 to 250 minutes, and in the subsequent preparation process, the accumulation of several practical experiences can omit the viscosity test step and directly enter the final vacuum defoaming process. Thereby, it can save 30-40 minutes, and the production time is greatly improved compared with the preparation time of about 5-8 hours of the conventional preparation process;
  • equipment wear is small: the invention only needs to vacuum the barrel in the final vacuum defoaming process, compared with the traditional process in the slurry preparation process, the stirring system has been kept vacuuming, resulting in the stirring process The heat is difficult to dissipate, the temperature of the slurry is easy to rise, and the effect is substantially improved.
  • the short-time vacuum treatment reduces the burden on the equipment and reduces equipment wear;
  • the solid content of the positive electrode slurry prepared by the invention is about 52-62%, which has the characteristics of high solid content and low viscosity compared with the conventional preparation process, so the amount of solvent used is correspondingly reduced. Reduces the energy required to evaporate and recover the solvent during subsequent coating processes;
  • the invention firstly stirs and disperses lithium cobaltate, conductive agent and binder to avoid agglomeration of conductive agent in the slurry.
  • high-viscosity stirring and dispersion are used, and the mechanical effect of the stirring paddle on the slurry is adopted.
  • the force (extrusion, collision, friction) is large, and it can achieve a good dispersion effect, and then the low-viscosity agitation is used to completely disperse the components.
  • the lithium battery prepared by using the lithium battery lithium cobaltate positive electrode slurry provided by the invention has low internal resistance, is not easy to generate heat, has high energy density, good cycle performance and long service life.
  • the preparation steps are as follows:
  • the test result is 7415Mpa ⁇ S, the value of the normal range is 5%, the total amount of the solvent is added, and the dispersion is stirred for 40 minutes, and the time is 20 minutes. And 40 minutes, scrape the slurry on the paddle and the barrel, and then test the viscosity of the slurry.
  • the test result is 5972Mpa ⁇ S, which meets the viscosity range requirement;
  • the barrel is evacuated, the degree of vacuum is -0.09 to -0.1 MPa, and the time is 30 minutes, that is, the positive electrode slurry prepared by the method of the invention is obtained, and the total consumption time is about 250 minutes.
  • the positive electrode slurry is coated, dried, rolled, and cut into positive electrode sheets, and then assembled with negative electrode sheets, separators, electrolytes, and battery casings, and then activated by charge and discharge.
  • Model 18650 cylindrical lithium cobalt oxide battery with an initial design capacity of 2000 mA.
  • the preparation takes about 7 hours, and according to the conventional production process of the lithium battery, a cylindrical lithium cobalt oxide battery of 18650 type with an initial design capacity of 2000 mA is obtained.
  • Example 1 The 18650 type cylindrical battery prepared in Example 1 and Comparative Example 1 was subjected to electrical property test, and charged and discharged at 1 C, and the cycle capacity retention rate was 500 times, and Example 1 was 93.17%, and Comparative Example 1 was 89.52%.
  • the energy density and internal resistance test comparison results are shown in Table 1.
  • the solvent NMP is 90 of the total amount of the above components. %.
  • the preparation steps are as follows:
  • the barrel is evacuated, the degree of vacuum is -0.09 to -0.1 MPa, and the time is 15 minutes, that is, the positive electrode slurry prepared by the method of the invention is obtained, and the total consumption time is about 165 minutes.
  • the positive electrode slurry is coated, dried, rolled, and cut into positive electrode sheets, and then assembled with negative electrode sheets, separators, electrolytes, and battery casings, and then activated by charge and discharge.
  • Model 18650 cylindrical lithium cobalt oxide battery with an initial design capacity of 2200 mA.
  • the preparation takes about 7 hours, and according to the conventional production process of lithium battery, a cylindrical lithium cobalt oxide battery of 18650 type with an initial design capacity of 2200 mA is obtained.
  • Example 2 The electrical properties of the 18650-type cylindrical battery prepared in Example 2 and Comparative Example 2 were tested and charged and discharged at 1 C, and the cycle capacity retention rate was 500 times, and Example 2 was 92.13%, and Comparative Example 2 was 88.79%.
  • the energy density and internal resistance test comparison results are shown in Table 1.
  • the lithium battery prepared by using the lithium cobaltate positive electrode slurry prepared by the method of the invention has higher energy density than the lithium battery produced by the conventional positive electrode slurry production process, and has an internal resistance. Both are lower than the lithium battery produced by the conventional positive electrode slurry production process.

Abstract

A preparation method for lithium battery lithium cobalt oxide positive-electrode slurry. Uniform dispersion of various components of slurry within a relatively short period of time is achieved by using the steps of powder dispersing, high-viscosity stirring, low-viscosity stirring, viscosity testing, vacuum defoaming, and the like. The prepared slurry is desirable in uniformity and excellent in stability; meanwhile, the adhesive power of a prepared battery pole piece is improved, so that the consistency and the electrochemical properties of the battery are improved. The preparation method has the advantages of short preparation time, small equipment abrasion, low energy consumption in production, good dispersion effect, and the like. The lithium battery that is prepared from the lithium battery lithium cobalt oxide positive-electrode slurry prepared by using the method is not easy to heat, and is low in internal resistance, high in energy density, desirable in cycle performance, and long in service life.

Description

一种钴酸锂正极浆料的制备方法Preparation method of lithium cobaltate positive electrode slurry 技术领域Technical field
本专利涉及锂离子电池领域，具体为一种钴酸锂正极材料浆料的制备工艺及方法。The patent relates to the field of lithium ion batteries, in particular to a preparation process and a method for a lithium cobaltate cathode material slurry.
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。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.
锂离子电池一般包括正极片、负极片、间隔于正极片和负极片之间的隔膜。正极极片包括正极集流体和涂布在正极集流体上的正极膜片，负极片包括负极集流体和涂布在负极集流体上的负极膜片。电极极片制备时，首先将活性物质(如钴酸锂、石墨等)、导电剂(如乙炔黑，碳纳米管、碳纤维等)、粘接剂(如聚偏氟乙烯、聚乙烯基吡咯烷酮、羧甲基纤维素钠、丁苯橡胶乳液等)和溶剂(如N-甲基吡咯烷酮、水等)一起制成电极浆料，再将其按要求涂覆在集流体表面，然后进行干燥，得到电池极片。A lithium ion battery generally includes a positive electrode sheet, a negative electrode sheet, and a separator interposed between the positive electrode sheet and the negative electrode sheet. The positive electrode tab includes a positive electrode current collector and a positive electrode film coated on the positive electrode current collector, and the negative electrode plate includes a negative electrode current collector and a negative electrode film coated on the negative electrode current collector. When preparing the electrode pole piece, firstly, an active material (such as lithium cobaltate, graphite, etc.), a conductive agent (such as acetylene black, carbon nanotubes, carbon fiber, etc.), a binder (such as polyvinylidene fluoride, polyvinylpyrrolidone, Carboxymethylcellulose sodium, styrene-butadiene rubber emulsion, etc.) and a solvent (such as N-methylpyrrolidone, water, etc.) are used together to form an electrode slurry, which is then coated on the surface of the current collector as required, and then dried to obtain Battery pole piece.
其中电极浆料的性能对锂离子电池的性能有着重要的影响。电极浆料中各组分分散得越均匀，极片便具有越好的加工性能，且电极各处的阻抗分布均匀，在充放电时活性物质的作用可以发挥得越大，其平均克容量发挥将会有所提升，从而提升全电池的性能。The performance of the electrode paste has an important influence on the performance of the lithium ion battery. The more uniform the components in the electrode slurry are dispersed, the better the processing performance of the pole piece, and the uniform distribution of the impedance of the electrode. The effect of the active substance can be exerted during charging and discharging, and the average gram capacity is exerted. Will be improved to improve the performance of the full battery.
实际应用上，传统的正极浆料制备方法是将导电剂用粘结剂溶液进行高转速的双行星式分散，然后加入正极活性物质，进行一定时间的搅拌后得到最终正极浆料。此种方法首先对导电剂的分散需要长时间处理，耗时长且分散状态并不理想，尤其是对于采用碳纳米管(CNT)、石墨烯等为导电剂的浆料制备；其次传统工艺需要在浆料制备过程中，对搅拌体系一直保持抽真空状态，造成浆料体系内部温度易升高，同时又在外部加循环水进行冷却，因此对设备的要求和磨损都很高。以上导致浆料制备效率低、稳定性差、效果不理想，对后续极片的制备、锂电池的性能都会造成影响。In practical application, the conventional positive electrode slurry preparation method is to carry out high-speed double planetary dispersion of a conductive agent with a binder solution, and then add a positive electrode active material, and stir for a certain period of time to obtain a final positive electrode slurry. This method firstly requires a long time treatment for the dispersion of the conductive agent, which takes a long time and is not ideal in the dispersion state, especially for the preparation of a slurry using a carbon nanotube (CNT), graphene or the like as a conductive agent; the second conventional process needs to be During the preparation of the slurry, the stirring system is kept under vacuum, which causes the internal temperature of the slurry system to rise easily, and at the same time, externally added circulating water for cooling, so the requirements and wear of the equipment are high. The above results in low slurry preparation efficiency, poor stability, and unsatisfactory effect, which will affect the preparation of the subsequent pole piece and the performance of the lithium battery.
发明内容Summary of the invention
为了克服现有技术中存在的问题，本发明的目的是提供一种锂电池钴酸锂正极浆料的制备方法，以实现在较短时间内对浆料各组分均匀分散，其制备出的浆料均匀性好，稳定性优异，同时其制备的电池极片粘附力得到提高，并因此提高电池的一致性及其电池的电化学性能。In order to overcome the problems existing in the prior art, an object of the present invention is to provide a method for preparing a lithium battery lithium cobaltate positive electrode slurry, which is capable of uniformly dispersing the components of the slurry in a relatively short time, and preparing the same. The slurry has good uniformity and excellent stability, and at the same time, the prepared battery sheet adhesion is improved, and thus the consistency of the battery and the electrochemical performance of the battery are improved.
为了实现上述发明目的，本发明采用如下所述的技术方案：In order to achieve the above object, the present invention adopts the technical solution as described below:
1、分散粉体：将钴酸锂、导电剂、粘结剂按比例加入搅拌桶搅拌分散，时间为30～40分钟，并在时间1/2和结束时，刮搅拌桨和桶体上的粉体；1. Disperse powder: Add lithium cobalt oxide, conductive agent and binder to the mixing tank in proportion and stir for 30 to 40 minutes. At time 1/2 and at the end, scrape the paddle and the barrel. Powder
2、高粘度搅拌：加入溶剂总量的55％～60％到上述搅拌后的粉体中，搅拌分散，时间为60～70分钟，并在时间1/3、2/3和结束时，刮搅拌桨和桶体上的浆料，浆料温度控制在25～35℃之间； 2. High-viscosity stirring: adding 55% to 60% of the total amount of the solvent to the stirred powder, stirring and dispersing for 60 to 70 minutes, and scraping at time 1/3, 2/3 and at the end Stir the slurry on the paddle and the barrel, and the slurry temperature is controlled between 25 and 35 ° C;
3、低粘度搅拌：加入溶剂总量的35～30％到上述高粘度搅拌后的浆料中，搅拌分散，时间为60～70分钟，并在时间1/3、2/3和结束时，刮搅拌桨和桶体上的浆料，浆料温度控制在25～35℃之间；3. Low-viscosity stirring: adding 35 to 30% of the total amount of the solvent to the above-mentioned high-viscosity stirred slurry, stirring and dispersing for 60 to 70 minutes, and at the time of 1/3, 2/3 and at the end, Scrape the paddle and the slurry on the barrel, and the slurry temperature is controlled between 25 and 35 ° C;
4、粘度测试：将上述步骤低粘度搅拌的浆料粘度进行粘度测试，如在正常范围4000～7000Mpa·S，直接进入下一步真空消泡；如超过上述范围，则添加溶剂总量的5％～10％，再搅拌分散，时间为30～40分钟，并在时间1/2和结束时，刮搅拌桨和桶体上的浆料，再检测一次浆料粘度，达到粘度范围要求即可进入下一步；4. Viscosity test: the viscosity of the slurry with low viscosity stirring in the above steps is tested for viscosity, such as in the normal range of 4000-7000 Mpa·S, directly into the next vacuum defoaming; if it exceeds the above range, 5% of the total amount of solvent is added. ~10%, stir and disperse for a period of 30 to 40 minutes, and at time 1/2 and at the end, scrape the slurry on the paddle and the barrel, and then test the viscosity of the slurry to reach the viscosity range. Next step;
5、真空消泡：在低速搅拌状态下，对桶体进行抽真空，真空度为-0.09～-0.1MPa，时间为15～30分钟，即得到本发明方法所制备的正极浆料。5. Vacuum defoaming: Under low-speed stirring, the barrel is evacuated, the degree of vacuum is -0.09 to -0.1 MPa, and the time is 15 to 30 minutes, that is, the positive electrode slurry prepared by the method of the invention is obtained.
上述步骤1中导电剂为导电炭黑、导电石墨、碳纳米管、碳纤维、石墨烯中的一种或多种混合物。The conductive agent in the above step 1 is one or a mixture of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers, and graphene.
上述步骤1中粘结剂为聚偏氟乙烯(PVDF)。The binder in the above step 1 is polyvinylidene fluoride (PVDF).
上述步骤2中溶剂为N-甲基吡咯烷酮(NMP)。The solvent in the above step 2 is N-methylpyrrolidone (NMP).
上述步骤1和步骤2中，钴酸锂、导电剂、粘结剂各组分的质量比依次为(90-97)：(1-4)：(1-5)，溶剂为上述各组分总重量的60％～90％。In the above steps 1 and 2, the mass ratio of each component of the lithium cobaltate, the conductive agent, and the binder is (90-97): (1-4): (1-5), and the solvent is the above components. 60% to 90% of the total weight.
上述各步骤中，搅拌设备是双行星真空搅拌机，浆料温度是利用向行星搅拌桶通入相应温度的恒温循环水的方法来控制的。In the above steps, the agitation device is a dual planetary vacuum agitator, and the slurry temperature is controlled by a method of introducing a constant temperature circulating water to the planetary agitating barrel at a corresponding temperature.
由于采用上述技术方案，本发明具有以下优越性：Due to the adoption of the above technical solutions, the present invention has the following advantages:
1、制备时间短：本发明正极浆料制备时间全程约为195～250分钟，且在后续制备过程中，通过几次实际经验的积累，可省略粘度测试步骤，直接进入最后真空消泡过程，由此又可节省30～40分钟，相比常规制备工艺约5～8小时的制备时间，大大提高了生产效率；1. Short preparation time: the preparation time of the positive electrode slurry of the invention is about 195 to 250 minutes, and in the subsequent preparation process, the accumulation of several practical experiences can omit the viscosity test step and directly enter the final vacuum defoaming process. Thereby, it can save 30-40 minutes, and the production time is greatly improved compared with the preparation time of about 5-8 hours of the conventional preparation process;
2、设备磨损小：本发明只在最后真空消泡过程中才需要对桶体进行抽真空，相比传统工艺需要在浆料制备过程中，对搅拌体系一直保持抽真空状态，造成搅拌过程中热量难散发，浆料温度易升高的弊端，具有实质性改善效果，短时间抽真空处理降低设备负担，减小设备磨损；2, equipment wear is small: the invention only needs to vacuum the barrel in the final vacuum defoaming process, compared with the traditional process in the slurry preparation process, the stirring system has been kept vacuuming, resulting in the stirring process The heat is difficult to dissipate, the temperature of the slurry is easy to rise, and the effect is substantially improved. The short-time vacuum treatment reduces the burden on the equipment and reduces equipment wear;
3、生产能耗低：本发明所制得的正极浆料固含量约为52～62％，相比常规制备工艺，具有高固含量、低粘度的特点，因此使用的溶剂量也相应减少，降低了后续涂布过程中对溶剂蒸发和回收所需的能耗；3. Low production energy consumption: the solid content of the positive electrode slurry prepared by the invention is about 52-62%, which has the characteristics of high solid content and low viscosity compared with the conventional preparation process, so the amount of solvent used is correspondingly reduced. Reduces the energy required to evaporate and recover the solvent during subsequent coating processes;
4、分散效果好：本发明先将钴酸锂、导电剂、粘结剂进行搅拌分散，避免了导电剂在浆料中产生团聚，前期采用高粘度搅拌分散，搅拌桨对浆料的机械作用力(挤压、碰撞、摩擦)大，能起到很好的分散效果，再采用低粘度搅拌，使各组分彻底被分散开。4. Good dispersion effect: The invention firstly stirs and disperses lithium cobaltate, conductive agent and binder to avoid agglomeration of conductive agent in the slurry. In the early stage, high-viscosity stirring and dispersion are used, and the mechanical effect of the stirring paddle on the slurry is adopted. The force (extrusion, collision, friction) is large, and it can achieve a good dispersion effect, and then the low-viscosity agitation is used to completely disperse the components.
采用本发明提供的锂电池钴酸锂正极浆料所制得的锂电池，内阻低，不易发热，而且能量密度高、循环性能好、使用寿命长。The lithium battery prepared by using the lithium battery lithium cobaltate positive electrode slurry provided by the invention has low internal resistance, is not easy to generate heat, has high energy density, good cycle performance and long service life.
具体实施方式detailed description
下面通过具体实施例，对本发明的技术方案作进一步的具体说明。The technical solution of the present invention will be further specifically described below through specific embodiments.
实施例1Example 1
以SP为导电剂，PVDF为粘结剂，按照LiCoO2：SP：PVDF＝95.7：2.3：2.0的质量比，溶剂NMP为上述各组分总量的65％。制备步骤如下：Taking SP as a conductive agent and PVDF as a binder, the solvent NMP was 65% of the total amount of the above components in accordance with the mass ratio of LiCoO 2 :SP:PVDF=95.7:2.3:2.0. The preparation steps are as follows:
1、将各组分加入搅拌桶搅拌分散，时间为40分钟，并在时间20分钟和40分钟时，刮搅拌桨和桶体上的粉体； 1. Add the components to the mixing tank and stir and disperse for 40 minutes, and scrape the powder on the paddle and the barrel at the time of 20 minutes and 40 minutes;
2、加入NMP总量的55％到上述搅拌后的粉体中，搅拌分散，时间为70分钟，并在时间20分钟、40分钟和60分钟时，刮搅拌桨和桶体上的浆料，浆料温度控制在25～35℃之间；2. Add 55% of the total amount of NMP to the stirred powder, stir and disperse for 70 minutes, and scrape the slurry on the paddle and the barrel at the time of 20 minutes, 40 minutes and 60 minutes. The slurry temperature is controlled between 25 and 35 ° C;
3、加入溶剂总量的35％到上述高粘度搅拌后的浆料中，搅拌分散，时间为60分钟，并在时间23分钟、46分钟和70分钟时，刮搅拌桨和桶体上的浆料，浆料温度控制在25～35℃之间；3. Add 35% of the total amount of the solvent to the above-mentioned high-viscosity stirred slurry, stir and disperse for 60 minutes, and scrape the paddle and the slurry on the barrel at the time of 23 minutes, 46 minutes, and 70 minutes. The temperature of the slurry is controlled between 25 and 35 ° C;
4、将上述步骤低粘度搅拌的浆料粘度进行粘度测试，测试结果为7415Mpa·S，超正常范围值，添加溶剂总量的5％，再搅拌分散，时间为40分钟，并在时间20分钟和40分钟时，刮搅拌桨和桶体上的浆料，再检测一次浆料粘度，测试结果为5972Mpa·S，达到粘度范围要求；4. Perform the viscosity test on the viscosity of the slurry with low viscosity stirring in the above steps. The test result is 7415Mpa·S, the value of the normal range is 5%, the total amount of the solvent is added, and the dispersion is stirred for 40 minutes, and the time is 20 minutes. And 40 minutes, scrape the slurry on the paddle and the barrel, and then test the viscosity of the slurry. The test result is 5972Mpa·S, which meets the viscosity range requirement;
5、在低速搅拌状态下，对桶体进行抽真空，真空度为-0.09～-0.1MPa，时间为30分钟，即得到本发明方法所制备的正极浆料，共耗时约250分钟。5. Under low-speed stirring, the barrel is evacuated, the degree of vacuum is -0.09 to -0.1 MPa, and the time is 30 minutes, that is, the positive electrode slurry prepared by the method of the invention is obtained, and the total consumption time is about 250 minutes.
按照锂电池常规生产工艺，将正极浆料经涂布、干燥、轧膜、分切制成正极片，然后与负极片、隔膜、电解液、电池外壳进行组装成，经充放电活化后制得18650型、初始设计容量为2000mA的圆柱型钴酸锂电池。According to the conventional production process of lithium battery, the positive electrode slurry is coated, dried, rolled, and cut into positive electrode sheets, and then assembled with negative electrode sheets, separators, electrolytes, and battery casings, and then activated by charge and discharge. Model 18650, cylindrical lithium cobalt oxide battery with an initial design capacity of 2000 mA.
对比例1Comparative example 1
按照常规的钴酸锂正极浆料生产工艺，制备耗时约7个小时，按照锂电池常规生产工艺，制得18650型、初始设计容量为2000mA的圆柱型钴酸锂电池。According to the conventional lithium cobaltate positive electrode slurry production process, the preparation takes about 7 hours, and according to the conventional production process of the lithium battery, a cylindrical lithium cobalt oxide battery of 18650 type with an initial design capacity of 2000 mA is obtained.
对实施例1和对比例1所制得的18650型圆柱电池进行电学性能测试，其在1C下充放,500次的循环容量保持率，实施例1为93.17％，对比例1为89.52％，能量密度及内阻测试对比结果如表1所示。The 18650 type cylindrical battery prepared in Example 1 and Comparative Example 1 was subjected to electrical property test, and charged and discharged at 1 C, and the cycle capacity retention rate was 500 times, and Example 1 was 93.17%, and Comparative Example 1 was 89.52%. The energy density and internal resistance test comparison results are shown in Table 1.
实施例2Example 2
以SP和KS-6为导电剂，PVDF为粘结剂，按照LiCoO2：SP：KS-6：PVDF＝93：2.2：1.3：3.5的质量比，溶剂NMP为上述各组分总量的90％。制备步骤如下：Taking SP and KS-6 as conductive agents and PVDF as binder, according to the mass ratio of LiCoO 2 :SP:KS-6:PVDF=93:2.2:1.3:3.5, the solvent NMP is 90 of the total amount of the above components. %. The preparation steps are as follows:
1、将各组分加入搅拌桶搅拌分散，时间为30分钟，并在时间15分钟和30分钟时，刮搅拌桨和桶体上的粉体；1. Add the components to the mixing tank and stir and disperse for 30 minutes, and scrape the powder on the paddle and the barrel at the time of 15 minutes and 30 minutes;
2、加入NMP总量的60％到上述搅拌后的粉体中，搅拌分散，时间为60分钟，并在时间20分钟、40分钟和60分钟时，刮搅拌桨和桶体上的浆料，浆料温度控制在25～35℃之间；2. Add 60% of the total amount of NMP to the stirred powder, stir and disperse for 60 minutes, and scrape the slurry on the paddle and the barrel at the time of 20 minutes, 40 minutes and 60 minutes. The slurry temperature is controlled between 25 and 35 ° C;
3、加入溶剂总量的30％到上述高粘度搅拌后的浆料中，搅拌分散，时间为60分钟，并在时间20分钟、40分钟和60分钟时，刮搅拌桨和桶体上的浆料，浆料温度控制在25～35℃之间；3. Add 30% of the total amount of the solvent to the above-mentioned high-viscosity stirred slurry, stir and disperse for 60 minutes, and scrape the paddle and the slurry on the barrel at the time of 20 minutes, 40 minutes and 60 minutes. The temperature of the slurry is controlled between 25 and 35 ° C;
4、将上述步骤低粘度搅拌的浆料粘度进行粘度测试，测试结果为5911Mpa·S，属于正常范围值，达到要求；4. Perform the viscosity test on the viscosity of the slurry with low viscosity stirring in the above steps. The test result is 5911 Mpa·S, which is a normal range value and meets the requirements;
5、在低速搅拌状态下，对桶体进行抽真空，真空度为-0.09～-0.1MPa，时间为15分钟，即得到本发明方法所制备的正极浆料，共耗时约165分钟。5. Under low-speed stirring, the barrel is evacuated, the degree of vacuum is -0.09 to -0.1 MPa, and the time is 15 minutes, that is, the positive electrode slurry prepared by the method of the invention is obtained, and the total consumption time is about 165 minutes.
按照锂电池常规生产工艺，将正极浆料经涂布、干燥、轧膜、分切制成正极片，然后与负极片、隔膜、电解液、电池外壳进行组装成，经充放电活化后制得18650型、初始设计容量为2200mA的圆柱型钴酸锂电池。According to the conventional production process of lithium battery, the positive electrode slurry is coated, dried, rolled, and cut into positive electrode sheets, and then assembled with negative electrode sheets, separators, electrolytes, and battery casings, and then activated by charge and discharge. Model 18650, cylindrical lithium cobalt oxide battery with an initial design capacity of 2200 mA.
对比例2Comparative example 2
按照常规的钴酸锂正极浆料生产工艺，制备耗时约7个小时，按照锂电池常规生产工艺，制得18650型、初始设计容量为2200mA的圆柱型钴酸锂电池。 According to the conventional production process of lithium cobaltate positive electrode slurry, the preparation takes about 7 hours, and according to the conventional production process of lithium battery, a cylindrical lithium cobalt oxide battery of 18650 type with an initial design capacity of 2200 mA is obtained.
对实施例2和对比例2所制得的18650型圆柱电池进行电学性能测试，其在1C下充放,500次的循环容量保持率，实施例2为92.13％，对比例2为88.79％，能量密度及内阻测试对比结果如表1所示。The electrical properties of the 18650-type cylindrical battery prepared in Example 2 and Comparative Example 2 were tested and charged and discharged at 1 C, and the cycle capacity retention rate was 500 times, and Example 2 was 92.13%, and Comparative Example 2 was 88.79%. The energy density and internal resistance test comparison results are shown in Table 1.
表1.各实施例与对比例的能量密度及内阻测试对比结果Table 1. Comparison of energy density and internal resistance test of each example and comparative example
项目project 能量密度(Wh/kg)Energy density (Wh/kg) 内阻(mΩ)Internal resistance (mΩ)
实施例1Example 1 167.6167.6 40.240.2
对比例1Comparative example 1 160.1160.1 43.543.5
实施例2Example 2 178.6178.6 38.738.7
对比例2Comparative example 2 171.3171.3 42.142.1
从上表可以看出，采用本发明方法制备的钴酸锂正极浆料所制得的锂电池，在能量密度上均高于常规正极浆料生产工艺所制得的锂电池，在内阻上均低于常规正极浆料生产工艺所制得的锂电池。It can be seen from the above table that the lithium battery prepared by using the lithium cobaltate positive electrode slurry prepared by the method of the invention has higher energy density than the lithium battery produced by the conventional positive electrode slurry production process, and has an internal resistance. Both are lower than the lithium battery produced by the conventional positive electrode slurry production process.
以上显示和描述了本发明的基本原理和主要特征及本发明的优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内，本发明要求保护范围由所附的权利要求书及其等效物界定。 The basic principles and main features of the present invention and the advantages of the present invention are shown and described above, and those skilled in the art should understand that the present invention is not limited by the above embodiments, and that the above embodiments and descriptions are merely illustrative of the present invention. The present invention is subject to various modifications and improvements without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The requirements and their equivalents are defined.

Claims (6)

  1. 一种钴酸锂正极浆料的制备方法，其制备步骤如下：A preparation method of a lithium cobaltate positive electrode slurry, the preparation steps are as follows:
    (1)分散粉体：将钴酸锂、导电剂、粘结剂按比例加入搅拌桶搅拌分散，时间为30～40分钟，并在时间1/2和结束时，刮搅拌桨和桶体上的粉体；(1) Dispersing powder: Lithium cobaltate, conductive agent and binder are added to the mixing tank in proportion and stirred for 30 to 40 minutes, and at the end of time 1/2 and at the end, the paddle and the barrel are scraped. Powder
    (2)高粘度搅拌：加入溶剂总量的55％～60％到上述搅拌后的粉体中，搅拌分散，时间为60～70分钟，并在时间1/3、2/3和结束时，刮搅拌桨和桶体上的浆料，浆料温度控制在25～35℃之间；(2) High-viscosity stirring: adding 55% to 60% of the total amount of the solvent to the stirred powder, stirring and dispersing for 60 to 70 minutes, and at the time of 1/3, 2/3 and at the end, Scrape the paddle and the slurry on the barrel, and the slurry temperature is controlled between 25 and 35 ° C;
    (3)低粘度搅拌：加入溶剂总量的35～30％到上述高粘度搅拌后的浆料中，搅拌分散，时间为60～70分钟，并在时间1/3、2/3和结束时，刮搅拌桨和桶体上的浆料，浆料温度控制在25～35℃之间；(3) Low-viscosity stirring: adding 35 to 30% of the total amount of the solvent to the above-mentioned high-viscosity stirred slurry, stirring and dispersing for 60 to 70 minutes, and at the time of 1/3, 2/3 and the end , scraping the slurry on the paddle and the barrel, the temperature of the slurry is controlled between 25 and 35 ° C;
    (4)粘度测试：将上述步骤低粘度搅拌的浆料粘度进行粘度测试，如在正常范围4000～7000Mpa·S，直接进入下一步真空消泡；如超过上述范围，则添加溶剂总量的5％～10％，再搅拌分散，时间为30～40分钟，并在时间1/2和结束时，刮搅拌桨和桶体上的浆料，再检测一次浆料粘度，达到粘度范围要求即可进入下一步；(4) Viscosity test: the viscosity of the slurry with low viscosity stirring in the above steps is tested for viscosity, such as in the normal range of 4000-7000 Mpa·S, directly into the next vacuum defoaming; if the above range is exceeded, the total amount of solvent is added 5 %～10%, stir and disperse for 30-40 minutes, and at time 1/2 and at the end, scrape the slurry on the paddle and barrel, and then test the viscosity of the slurry to reach the viscosity range. Go to the next step;
    (5)真空消泡：在低速搅拌状态下，对桶体进行抽真空，真空度为-0.09～-0.1MPa，时间为15～30分钟，即得到本发明方法所制备的正极浆料。(5) Vacuum defoaming: Under low-speed stirring, the barrel is evacuated, the degree of vacuum is -0.09 to -0.1 MPa, and the time is 15 to 30 minutes, that is, the positive electrode slurry prepared by the method of the present invention is obtained.
  2. 根据权利要求1所述的一种钴酸锂正极浆料的制备方法，其特征是，上述步骤(1)中导电剂为导电炭黑、导电石墨、碳纳米管、碳纤维、石墨烯中的一种或多种混合物。The method for preparing a lithium cobaltate positive electrode slurry according to claim 1, wherein the conductive agent in the step (1) is one of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers, and graphene. One or more mixtures.
  3. 根据权利要求1所述的一种钴酸锂正极浆料的制备方法，其特征是，上述步骤(1)中粘结剂为聚偏氟乙烯。The method for preparing a lithium cobaltate positive electrode slurry according to claim 1, wherein the binder in the step (1) is polyvinylidene fluoride.
  4. 根据权利要求1所述的一种钴酸锂正极浆料的制备方法，其特征是，上述步骤(2)中溶剂为N-甲基吡咯烷酮。The method for producing a lithium cobaltate positive electrode slurry according to claim 1, wherein the solvent in the step (2) is N-methylpyrrolidone.
  5. 根据权利要求1所述的一种钴酸锂正极浆料的制备方法，其特征是，上述步骤(1)和步骤(2)中，钴酸锂、导电剂、粘结剂各组分的质量比依次为(90-97)：(1-4)：(1-5)，溶剂为上述各组分总重量的60％～90％。The method for preparing a lithium cobaltate positive electrode slurry according to claim 1, wherein the quality of each component of the lithium cobaltate, the conductive agent and the binder in the above steps (1) and (2) The ratio is (90-97): (1-4): (1-5), and the solvent is 60% to 90% of the total weight of each component described above.
  6. 根据权利要求1所述的一种钴酸锂正极浆料的制备方法，其特征是，上述各步骤中，搅拌设备是双行星真空搅拌机，浆料温度是利用向行星搅拌桶通入相应温度的恒温循环水的方法来控制的。 The method for preparing a lithium cobaltate positive electrode slurry according to claim 1, wherein in the above steps, the stirring device is a double planetary vacuum agitator, and the slurry temperature is obtained by introducing a corresponding temperature into the planetary mixing drum. The method of constant temperature circulating water is controlled.
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CN104201325A (en) * 2014-08-20 2014-12-10 浙江中科立德新材料有限公司 Novel lithium ion battery homogenizing and stirring process
CN104577071A (en) * 2015-01-28 2015-04-29 山东齐星新能源科技有限责任公司 Dry-powder pulping method of lithium-ion battery
CN104638229A (en) * 2015-01-30 2015-05-20 上海航天电源技术有限责任公司 Dry-blending hard-melting preparation method for electrode slurry of automobile power lithium ion battery
CN105185951A (en) * 2015-08-24 2015-12-23 深圳市斯诺实业发展有限公司 Preparation method of lithium battery cathode slurry
CN105047858A (en) * 2015-08-25 2015-11-11 田东 Preparation method for lithium cobalt oxide cathode slurry
CN105161709A (en) * 2015-08-25 2015-12-16 田东 Preparation method of lithium manganate cathode slurry
CN105161676A (en) * 2015-08-25 2015-12-16 田东 Preparation method for lithium iron phosphate cathode slurry

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CN113036230A (en) * 2021-03-18 2021-06-25 广东邦普循环科技有限公司 Preparation method and application of lithium cobaltate soft package battery
CN113036230B (en) * 2021-03-18 2023-01-13 广东邦普循环科技有限公司 Preparation method and application of lithium cobaltate soft package battery
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