WO2016082672A1 - Aqueous coating method of high-voltage lithium cobalt oxide positive electrode material - Google Patents

Aqueous coating method of high-voltage lithium cobalt oxide positive electrode material Download PDF

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WO2016082672A1
WO2016082672A1 PCT/CN2015/093823 CN2015093823W WO2016082672A1 WO 2016082672 A1 WO2016082672 A1 WO 2016082672A1 CN 2015093823 W CN2015093823 W CN 2015093823W WO 2016082672 A1 WO2016082672 A1 WO 2016082672A1
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ball mill
cobalt oxide
lithium cobalt
slurry
lithium cobaltate
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PCT/CN2015/093823
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French (fr)
Chinese (zh)
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尹雄鸽
李魁
周贵海
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南通瑞翔新材料有限公司
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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
    • H01M4/36—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
    • 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 invention belongs to the technical field of lithium batteries, and particularly relates to a water coating method for a high voltage lithium cobaltate cathode material.
  • lithium cobalt oxide is widely used because of its high working voltage and energy density, easy synthesis, and rapid charge and discharge.
  • Charging voltage is above 4.3V
  • the structural stability and safety performance of lithium cobaltate have obvious defects.
  • the current method is surface coating.
  • a layer of material is uniformly coated on the surface of the lithium cobaltate cathode material, which can effectively prevent the direct contact between the active material and the electrolyte, thereby effectively inhibiting the dissolution of Co in the material and improving the stability of the active material of the cathode. , thereby improving the cycle performance of the lithium ion battery.
  • the coating process used mainly includes dry coating and wet coating.
  • Different coating processes have a direct influence on the structure of LiCoO2, and the performance of the obtained LiCoO2 is also different.
  • the dry coating has the problem of uneven coating.
  • an organic solvent such as ethanol is used as the medium, which has the disadvantages of high production cost, high risk, and difficulty in industrialization.
  • the wet coating using pure water as a medium is The above problems can be avoided, and in order to further reduce the cost, a simple inorganic metal compound can be used for coating.
  • Citride 201310023937.6 discloses a coating process of lithium cobaltate, which is obtained by adding a metal ionic compound and a water-soluble organic substance to a slurry by a water ball, and then adding a lithium silicate and a water ball to obtain a secondary slurry in a slurry. The secondary slurry is dried and calcined to obtain a coated lithium cobaltate material.
  • the process has the following disadvantages: (1) the primary slurry is a suspension, and the metal ion compound is prone to sedimentation during the ball milling process due to the insufficient complexing ability of the simple organic substance to the water-insoluble metal ion compound, so that the coating process is in the process of coating. Segregation of metal ion compounds is liable to occur, resulting in a problem of uneven coating. (2) Due to the limited complexation of simple organic matter, a large amount of organic matter is used in the preparation of the slurry. The total molar amount of the water-soluble organic matter in the patent is 50-70% of the molar amount of lithium cobaltate, and the organic substance is subsequently calcined.
  • Decomposition into CO2 and H2O in the process does not produce an effect on the performance improvement of lithium cobaltate, and the large use of organic matter is a waste of raw materials.
  • the process requires mixing of metal ion compounds and water-soluble organic substances before making a slurry, which increases the process and does not utilize industrial production.
  • the ball milling time of the primary slurry of the process is 2 ⁇ 5h
  • the ball milling time of the secondary slurry is 6 ⁇ 12h
  • the ball milling time is long, which is not conducive to industrial production, and the long-term ball milling wears large equipment and increases the introduction of foreign matter.
  • the long-time ball milling of the secondary slurry may cause damage to the surface morphology and internal structure of the lithium cobaltate particles, that is, the particles mentioned in the patent have finer particle size, thereby affecting the physical and electrochemical properties of the product.
  • the object of the present invention is to provide a water-based coating method for a high-voltage lithium cobaltate cathode material, which has simple steps and low cost, and is suitable for industrial mass production, and the obtained lithium cobaltate product has uniform coating and electrochemical Good performance and other advantages.
  • the slurry is pumped into a vacuum dryer through a mortar pump for drying and drying.
  • the temperature is 100-200 ° C, and the drying time is 2-5 h;
  • step d The dried material in step d is added to the kiln for secondary sintering to ensure that the secondary sintering temperature is 600-900 ° C, and the secondary sintering time is 5-20 h;
  • step e The second sintered material in step e is sieved and iron removed to obtain the desired material.
  • the metal ion compound in the step b is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, titanium hydroxide, manganese hydroxide, nickel hydroxide, vanadium hydroxide, barium hydroxide, and tin hydroxide. Or a variety.
  • the dispersing agent in the step b is selected from one or more of polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyacrylic acid and the like.
  • the water-based coating method of the high-voltage lithium cobaltate cathode material disclosed by the invention is dispersed by using a highly polymerized organic dispersant in the preparation of the primary slurry, which can significantly reduce the use of organic substances and prevent the precipitation of metal ion compounds.
  • the highly polymerized dispersant can form an adsorption layer on the surface of the solid particles, increasing the charge on the surface of the solid particles, increasing the reaction force between the particles forming the steric hindrance, and the solid particles are separated by the electrostatic repulsion, thereby preventing the solid particles.
  • Agglomeration occurs, the system is uniform, the suspension performance is increased, and the precipitation is not precipitated, so that the physicochemical properties of the whole system are the same, so that the dispersing agent can stably disperse the solid particles in the liquid.
  • the water-based coating method of the high-voltage lithium cobaltate cathode material disclosed by the invention has the following advantages:
  • the coating material of the invention adopts a common metal ion compound, does not need to be dissolved, can greatly reduce the production cost, and the process step is also simpler.
  • the metal ion compound and the water-soluble polymer dispersant are ball-milled in water, and the metal ion compound and the water-soluble organic substance are complexed together by using the energy generated by the ball milling and the strong dispersing agent of the polymer dispersing agent to make the metal Ionic compounds and water-soluble organic substances can be uniformly dispersed to prevent water solubility
  • the metal ion compound precipitates, which is beneficial to improve the uniformity of the coating.
  • the complexing of the polymer dispersant and the special circulation device of the ball mill ensure that the metal ion compound and the dispersant can be uniformly dispersed around the lithium cobaltate particles, thereby improving the uniformity of the coating, in the cobalt acid.
  • the components can be kept uniform and stable, avoiding segregation of metal ion compounds in the secondary sintering process, preventing element precipitation and ensuring the electrochemical performance of the coated lithium cobalt oxide.
  • the surface of the lithium cobaltate is coated with a dense oxide to avoid direct contact between the lithium cobaltate and the electrolyte, reduce the capacity loss, improve the cycle performance of the material, and satisfy the use of lithium cobaltate at a high voltage of >4.35V.
  • the ball milling time is short, the slurry preparation and drying process can be carried out continuously, the process is simple, and the industrial production is convenient.
  • the invention removes iron in the ball milling process and the secondary sintering, effectively improves the product quality and ensures the electrochemical performance of the product.
  • Example 1 is an SEM spectrum of a finished lithium cobalt oxide coating in Example 1;
  • Example 2 is an EDS spectrum of the finished lithium cobalt oxide coating in Example 1;
  • Figure 3 is an XRD pattern of the finished lithium cobalt oxide coating in Example 1;
  • Example 4 is a first charge and discharge diagram of a button battery fabricated in the coated lithium cobalt oxide product of Example 1.
  • Example 5 is a graph showing the rate performance of a button battery produced by coating the finished lithium cobalt oxide product in Example 1;
  • Fig. 6 is a graph showing the cycle performance of a button battery produced by coating the finished lithium cobalt oxide product in Example 1.
  • the water coating method of a voltage lithium cobaltate cathode material disclosed by the invention comprises the following process steps:
  • the slurry is pumped into a vacuum dryer through a mortar pump for drying, the drying temperature is 100-200 ° C, and the drying time is 2-5 h;
  • step d The dried material in step d is added to the kiln for secondary sintering to ensure that the secondary sintering temperature is 600-900 ° C, and the secondary sintering time is 5-20 h;
  • step e The second sintered material in step e is sieved and iron removed to obtain the desired material.
  • the metal ion compound is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, titanium hydroxide, manganese hydroxide, nickel hydroxide, vanadium hydroxide, barium hydroxide, tin hydroxide, and the like.
  • the dispersing agents in the step b are one or more selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyacrylic acid and the like.
  • the water system coating method of the high voltage lithium cobaltate cathode material disclosed by the invention has the following specific steps:
  • the prepared secondary slurry is driven into a vacuum dryer by a mortar pump for drying, the drying temperature is 100 ° C, and the drying time is 3 h;
  • the dried material is added to the kiln for secondary sintering, the secondary sintering temperature is 850 ° C, and the secondary sintering time is 10 h;
  • the material after secondary sintering is further sieved and iron removed to obtain the desired material.
  • the water system coating method of the high voltage lithium cobaltate cathode material disclosed by the invention has the following specific steps:
  • the secondary slurry is driven into a vacuum dryer by a mortar pump for drying, the drying time is 150 ° C, and the drying time is 3 h;
  • the dried material is added to the kiln for secondary sintering.
  • the secondary sintering temperature was 800 ° C, and the secondary sintering time was 12 h.
  • the material after secondary sintering is further sieved and iron removed to obtain the desired material.
  • the water system coating method of the high voltage lithium cobaltate cathode material disclosed by the invention has the following specific steps:
  • the secondary slurry is driven into a vacuum dryer by a mortar pump for drying, the drying time is 180 ° C, and the drying time is 2 h;
  • the dried material is added to the kiln for secondary sintering.
  • the secondary sintering temperature was 850 ° C, and the secondary sintering time was 12 h.
  • the material after secondary sintering is further sieved and iron removed to obtain the desired material.
  • the surface morphology of the coated lithium cobalt oxide product was observed by scanning electron microscopy.
  • the microscopic morphology obtained is shown in Fig. 1. It can be seen from Fig. 1 that the coated lithium cobaltate particles are single crystal particles without agglomeration. The surface of the particles is smooth.
  • the particle surface of the lithium cobaltate product was characterized by an energy spectrum analyzer (EDS). It can be seen from the EDS spectrum that the constituent elements of lithium cobaltate are uniformly distributed, and Al is uniformly coated on the surface of the particle.
  • EDS energy spectrum analyzer
  • X-ray diffractometry was used to analyze the phase of the coated lithium cobalt oxide product.
  • the obtained spectrum is shown in Fig. 2.
  • the XRD spectrum of the coated lithium cobalt oxide and the standard spectrum of lithium cobaltate The one-to-one correspondence shows that the lithium cobaltate has good crystallinity and good crystal structure, and the coated lithium cobalt oxide crystal phase is single and complete, and no impurity phase is generated.
  • the charge-discharge test was carried out under the charge and discharge conditions of 0.1C, and the first charge-discharge curve obtained is shown in Fig. 4.
  • the first discharge specific capacity can reach 192.1 mA ⁇ h/g, and the first charge-discharge efficiency is 93.1%;
  • the first discharge specific capacity can reach 187.4mA ⁇ h/g, the first charge and discharge efficiency is 94.3%, and the discharge specific capacity is about 30% higher than the conventional lithium cobaltate (3.0 ⁇ 4.3V).
  • the rate performance tests were carried out at 0.1 C, 0.2 C, 0.5 C, 0.8 C, 1 C, 2 C and 5 C, respectively, and the obtained rate performance is shown in FIG. 5 .
  • the specific discharge capacity at 5C can reach 182.4mA ⁇ h/g, and the capacity ratio of 5C/0.1C is 95.10%.
  • the specific discharge capacity at 5C can reach 179.7mA ⁇ h/g, 5C.
  • the capacity ratio of /0.1 C is 95.64%, and the material of the present invention has excellent rate performance.
  • the cycle test was carried out in a voltage range of 3.0 to 4.5 V at a charge/discharge rate of 1 C/1 C, and the obtained cycle test chart is shown in Fig. 6.
  • the capacity retention rate after 94 cycles was 94.5%; at 45 ° C, the capacity retention after 100 cycles was 90.4%.
  • the material of the present invention is excellent in rate performance at normal temperature and high temperature.

Abstract

Disclosed is an aqueous coating method for a high-voltage lithium cobalt oxide positive electrode material. Specifically steps comprise: weighing and taking pure water and adding the pure water to a ball mill to perform ball milling, after ball milling is complete, starting a cycle, and then separately weighing and taking a dispersant and a metal ion compound and adding the dispersant and the metal ion compound to the ball mill to perform cyclic ball milling and dispersion, to complete preparation of a primary slurry; then weighing and taking lithium cobalt oxide and adding the lithium cobalt oxide to the ball mill to perform ball milling and dispersion, to complete preparation of a secondary slurry; after dispersion, the slurry is added to a vacuum drying machine by using a mortar pump to perform drying; and after drying, adding the material to a kiln to perform secondary sintering; and performing screening and metal elimination on the material after secondary sintering, to obtain a required material. For the preparation method disclosed in the present invention, a layer of oxide is coated on a surface of lithium cobalt oxide, thereby improving charging and discharging voltages of a lithium cobalt oxide positive electrode material, and overcoming a defect of undesirable cycling stability of the material during high-voltage charging and discharging, so that the material of the present invention can be used as a 4.4-V positive electrode lithium cobalt oxide material of a lithium ion battery.

Description

一种高电压钴酸锂正极材料的水系包覆方法Water coating method for high voltage lithium cobaltate cathode material 技术领域Technical field
本发明属于锂电池技术领域，特别涉及一种高电压钴酸锂正极材料的水系包覆方法。The invention belongs to the technical field of lithium batteries, and particularly relates to a water coating method for a high voltage lithium cobaltate cathode material.
背景技术Background technique
在锂离子正极材料中，钴酸锂由于具有较高的工作电压和能量密度、易合成且可快速充放电，因此被广泛应用。但是在深度充放电情况下(充电电压在4.3V以上)，钴酸锂结构稳定性和安全性能存在明显缺陷。Among the lithium ion positive electrode materials, lithium cobalt oxide is widely used because of its high working voltage and energy density, easy synthesis, and rapid charge and discharge. However, in the case of deep charge and discharge (charging voltage is above 4.3V), the structural stability and safety performance of lithium cobaltate have obvious defects.
为了解决钴酸锂存在的上述问题，目前采取的方法为表面包覆。通过一定的包覆技术，在钴酸锂正极材料表面均匀的包覆一层材料，可以有效防止活性材料与电解液的直接接触，从而有效的抑制材料中Co溶出，提高正极活性材料的稳定性，进而提高锂离子电池的循环性能。In order to solve the above problems of lithium cobaltate, the current method is surface coating. Through a certain coating technology, a layer of material is uniformly coated on the surface of the lithium cobaltate cathode material, which can effectively prevent the direct contact between the active material and the electrolyte, thereby effectively inhibiting the dissolution of Co in the material and improving the stability of the active material of the cathode. , thereby improving the cycle performance of the lithium ion battery.
目前，采用的包覆工艺主要有干式包覆和湿式包覆，不同的包覆工艺对LiCoO2的结构有着直接的影响，所得到的LiCoO2的性能也不尽相同。干式包覆存在包覆不均匀的问题，湿法包覆中采用乙醇等有机溶剂作为介质，存在生产成本高、危险性高、不易于工业化等缺点，采用纯水作为介质的湿式包覆则能避免以上问题，且为了进一步降低成本，可采用简单的无机金属化合物进行包覆。At present, the coating process used mainly includes dry coating and wet coating. Different coating processes have a direct influence on the structure of LiCoO2, and the performance of the obtained LiCoO2 is also different. The dry coating has the problem of uneven coating. In the wet coating, an organic solvent such as ethanol is used as the medium, which has the disadvantages of high production cost, high risk, and difficulty in industrialization. The wet coating using pure water as a medium is The above problems can be avoided, and in order to further reduce the cost, a simple inorganic metal compound can be used for coating.
中国专利201310023937.6公开了一种钴酸锂的包覆工艺，将金属离子化合物与水溶性的有机物加水球磨得一次浆料，再在一次浆料中加入钴酸锂与水球磨得二次浆料，二次浆料经烘干、焙烧后得包覆后的钴酸锂材料。Chinese Patent 201310023937.6 discloses a coating process of lithium cobaltate, which is obtained by adding a metal ionic compound and a water-soluble organic substance to a slurry by a water ball, and then adding a lithium silicate and a water ball to obtain a secondary slurry in a slurry. The secondary slurry is dried and calcined to obtain a coated lithium cobaltate material.
该工艺存在以下缺点：(1)一次浆料为悬浮液，由于简单的有机物对非水溶性的金属离子化合物的络合能力不足，在球磨过程中金属离子化合物易发生沉降，从而包覆过程中容易发生金属离子化合物的离析，造成包覆不均匀的问题。 (2)由于简单有机物的络合作用有限，浆料制备过程中需使用到大量的有机物，专利中水溶性有机物总摩尔量为钴酸锂摩尔量的50～70％，该有机物在后续的焙烧过程中分解成为CO2和H2O，不会产生对钴酸锂的性能改进的作用，有机物的大量使用是对原料的浪费。(3)该工艺在制作一次浆料前还需进行金属离子化合物与水溶性有机物的混合，增加了工艺过程，不利用产业化生产。(4)该工艺的一次浆料球磨时间为2～5h，二次浆料的球磨时间6～12h，球磨时间长，不利于工业化生产，且长时间的球磨对设备的磨损大，增加异物引入产品的可能性。且二次浆料长时间的球磨，会对钴酸锂颗粒的表面形貌和内部结构造成破坏，即专利中提到的颗粒的粒度更细，从而影响到产品的物理和电化学性能。The process has the following disadvantages: (1) the primary slurry is a suspension, and the metal ion compound is prone to sedimentation during the ball milling process due to the insufficient complexing ability of the simple organic substance to the water-insoluble metal ion compound, so that the coating process is in the process of coating. Segregation of metal ion compounds is liable to occur, resulting in a problem of uneven coating. (2) Due to the limited complexation of simple organic matter, a large amount of organic matter is used in the preparation of the slurry. The total molar amount of the water-soluble organic matter in the patent is 50-70% of the molar amount of lithium cobaltate, and the organic substance is subsequently calcined. Decomposition into CO2 and H2O in the process does not produce an effect on the performance improvement of lithium cobaltate, and the large use of organic matter is a waste of raw materials. (3) The process requires mixing of metal ion compounds and water-soluble organic substances before making a slurry, which increases the process and does not utilize industrial production. (4) The ball milling time of the primary slurry of the process is 2~5h, the ball milling time of the secondary slurry is 6~12h, the ball milling time is long, which is not conducive to industrial production, and the long-term ball milling wears large equipment and increases the introduction of foreign matter. Product possibilities. Moreover, the long-time ball milling of the secondary slurry may cause damage to the surface morphology and internal structure of the lithium cobaltate particles, that is, the particles mentioned in the patent have finer particle size, thereby affecting the physical and electrochemical properties of the product.
发明内容Summary of the invention
本发明的目的在于提供一种高电压钴酸锂正极材料的水系包覆方法，该包覆工艺步骤简单，成本低，适合工业化大批量生产，得到的钴酸锂产品具有包覆均匀、电化学性能良好等优点。The object of the present invention is to provide a water-based coating method for a high-voltage lithium cobaltate cathode material, which has simple steps and low cost, and is suitable for industrial mass production, and the obtained lithium cobaltate product has uniform coating and electrochemical Good performance and other advantages.
本发明采用的技术方案：一种高电压钴酸锂正极材料的水系包覆方法，包括以下工艺步骤：The technical solution adopted by the invention: a water-based coating method for a high-voltage lithium cobaltate cathode material, comprising the following process steps:
a.以钴酸锂重量为基准，称取钴酸锂重量20％～40％的纯水，打入球磨机内球磨，完成后开启循环；a. based on the weight of lithium cobalt oxide, weigh 20% to 40% of the weight of lithium cobaltate, and enter the ball mill in the ball mill, after the completion of the cycle;
b.分别称取占钴酸锂重量的0.1％～0.5％的分散剂和金属离子占钴酸锂重量0.01％～1％的金属离子化合物，并将分散剂和金属离子化合物倒入球磨机内进行循环球磨和分散完成一次浆料的制备，同时确保一次球磨分散时间为0.5～2h；b. Weigh 0.1% to 0.5% of the weight of lithium cobaltate and 0.1% to 1% of metal ion compound by weight of lithium cobaltate, and pour the dispersant and metal ion compound into the ball mill. Cyclic ball milling and dispersion to complete the preparation of a slurry, while ensuring a ball mill dispersion time of 0.5 ~ 2h;
c.再称取100～200Kg的钴酸锂，加入球磨机内进行球磨和分散完成二次浆料的制备，确保二次球磨分散时间为1～2h；c. Weigh 100-200Kg of lithium cobaltate, add to the ball mill for ball milling and dispersion to complete the preparation of the secondary slurry, to ensure that the secondary ball mill dispersion time is 1 ~ 2h;
d.完成球磨分散后，将浆料通过砂浆泵打入真空干燥机内进行干燥，干燥 温度为100～200℃，干燥时间为2～5h；d. After the ball mill is dispersed, the slurry is pumped into a vacuum dryer through a mortar pump for drying and drying. The temperature is 100-200 ° C, and the drying time is 2-5 h;
e.步骤d中完成干燥的物料加入窑炉中进行二次烧结，确保二次烧结温度为600～900℃，二次烧结时间为5～20h；e. The dried material in step d is added to the kiln for secondary sintering to ensure that the secondary sintering temperature is 600-900 ° C, and the secondary sintering time is 5-20 h;
f.将步骤e中二次烧结后的物料进行过筛和除铁，得到所需材料。f. The second sintered material in step e is sieved and iron removed to obtain the desired material.
所述步骤b中所述金属离子化合物选取氢氧化镁、氢氧化铝、氢氧化锆、氢氧化钛、氢氧化锰、氢氧化镍、氢氧化钒、氢氧化铈、氢氧化锡等的一种或多种。The metal ion compound in the step b is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, titanium hydroxide, manganese hydroxide, nickel hydroxide, vanadium hydroxide, barium hydroxide, and tin hydroxide. Or a variety.
所述步骤b中分散剂选取聚乙烯醇、聚乙二醇、聚丙烯酰胺、聚丙烯酸等的一种或多种。The dispersing agent in the step b is selected from one or more of polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyacrylic acid and the like.
本发明所揭示的一种高电压钴酸锂正极材料的水系包覆方法，在一次浆料制备时采用高聚合的有机物分散剂进行分散，能显著减少有机物的使用，并防止金属离子化合物发生沉降，同时高聚合的分散剂能在固体颗粒的表面形成吸附层，使固体颗粒表面的电荷增加，提高形成立体阻碍的颗粒间的反作用力，固体颗粒之间因静电斥力而远离，从而防止固体颗粒发生团聚，使体系均匀，悬浮性能增加，不沉淀，使整个体系物化性质一样，故而使用分散剂能安定地分散液体中的固体颗粒。The water-based coating method of the high-voltage lithium cobaltate cathode material disclosed by the invention is dispersed by using a highly polymerized organic dispersant in the preparation of the primary slurry, which can significantly reduce the use of organic substances and prevent the precipitation of metal ion compounds. At the same time, the highly polymerized dispersant can form an adsorption layer on the surface of the solid particles, increasing the charge on the surface of the solid particles, increasing the reaction force between the particles forming the steric hindrance, and the solid particles are separated by the electrostatic repulsion, thereby preventing the solid particles. Agglomeration occurs, the system is uniform, the suspension performance is increased, and the precipitation is not precipitated, so that the physicochemical properties of the whole system are the same, so that the dispersing agent can stably disperse the solid particles in the liquid.
与现有技术相比，本发明所揭示的一种高电压钴酸锂正极材料的水系包覆方法，具有如下优势：Compared with the prior art, the water-based coating method of the high-voltage lithium cobaltate cathode material disclosed by the invention has the following advantages:
本发明包覆材料采用常用的金属离子化合物，不需要进行溶解，可大大降低生产成本，工艺步骤也更为简单。The coating material of the invention adopts a common metal ion compound, does not need to be dissolved, can greatly reduce the production cost, and the process step is also simpler.
本发明将金属离子化合物与水溶性的聚合物分散剂在水中球磨，利用球磨所产生的能量和聚合物分散剂强的络合，使金属离子化合物与水溶性有机物络合在一起，可使金属离子化合物与水溶性有机物能够均匀分散，防止非水溶性 的金属离子化合物发生沉降，有利于提高包覆的均匀性。In the invention, the metal ion compound and the water-soluble polymer dispersant are ball-milled in water, and the metal ion compound and the water-soluble organic substance are complexed together by using the energy generated by the ball milling and the strong dispersing agent of the polymer dispersing agent to make the metal Ionic compounds and water-soluble organic substances can be uniformly dispersed to prevent water solubility The metal ion compound precipitates, which is beneficial to improve the uniformity of the coating.
二次球磨过程中，聚合物分散剂的络合作用、球磨机特殊的循环装置设计，保证了金属离子化合物、分散剂能均匀分散在钴酸锂颗粒周围，提高包覆的均匀性，在钴酸锂后续的干燥、焙烧过程中可以保持各组分均一、稳定，避免金属离子化合物在二次烧结过程中产生偏析的现象，防止元素析出，保证包覆后的钴酸锂的电化学性能，在钴酸锂表面包覆一层致密的氧化物，从而避免钴酸锂与电解液的直接接触，减少容量损失，改善材料的循环性能，满足钴酸锂在＞4.35V高电压下的使用。In the secondary ball milling process, the complexing of the polymer dispersant and the special circulation device of the ball mill ensure that the metal ion compound and the dispersant can be uniformly dispersed around the lithium cobaltate particles, thereby improving the uniformity of the coating, in the cobalt acid. During the subsequent drying and roasting of lithium, the components can be kept uniform and stable, avoiding segregation of metal ion compounds in the secondary sintering process, preventing element precipitation and ensuring the electrochemical performance of the coated lithium cobalt oxide. The surface of the lithium cobaltate is coated with a dense oxide to avoid direct contact between the lithium cobaltate and the electrolyte, reduce the capacity loss, improve the cycle performance of the material, and satisfy the use of lithium cobaltate at a high voltage of >4.35V.
球磨时间短，浆料制作和干燥过程可连续进行，工艺简单，便于产业化生产。The ball milling time is short, the slurry preparation and drying process can be carried out continuously, the process is simple, and the industrial production is convenient.
本发明在球磨过程和二次烧结后均进行了除铁，有效的改善了产品品质，保证产品的电化学性能。The invention removes iron in the ball milling process and the secondary sintering, effectively improves the product quality and ensures the electrochemical performance of the product.
附图说明DRAWINGS
图1是实施例1中包覆后钴酸锂成品的SEM图谱；1 is an SEM spectrum of a finished lithium cobalt oxide coating in Example 1;
图2是实施例1中包覆后钴酸锂成品的EDS图谱；2 is an EDS spectrum of the finished lithium cobalt oxide coating in Example 1;
图3是实施例1中包覆后钴酸锂成品的XRD图；Figure 3 is an XRD pattern of the finished lithium cobalt oxide coating in Example 1;
图4是实施例1中包覆后钴酸锂成品的制作的扣式电池的首次充放电图；4 is a first charge and discharge diagram of a button battery fabricated in the coated lithium cobalt oxide product of Example 1.
图5是实施例1中包覆后钴酸锂成品的制作的扣式电池的倍率性能图；5 is a graph showing the rate performance of a button battery produced by coating the finished lithium cobalt oxide product in Example 1;
图6是实施例1中包覆后钴酸锂成品的制作的扣式电池的循环性能图。Fig. 6 is a graph showing the cycle performance of a button battery produced by coating the finished lithium cobalt oxide product in Example 1.
具体实施方式detailed description
下面将以具体实施例对本发明的技术方案进行清楚、完整的描述。The technical solutions of the present invention will be clearly and completely described below by way of specific embodiments.
本发明所揭示的一种电压钴酸锂正极材料的水系包覆方法，包括以下工艺步骤：The water coating method of a voltage lithium cobaltate cathode material disclosed by the invention comprises the following process steps:
a.以钴酸锂重量为基准，称取钴酸锂重量20％～40％的纯水，打入球磨机内 球磨，完成后开启循环；a. Based on the weight of lithium cobalt oxide, weigh 20% to 40% of the weight of lithium cobaltate and pump it into the ball mill. Ball milling, after the completion of the cycle;
b.分别称取占钴酸锂重量的0.1％～0.5％的分散剂和金属离子占钴酸锂重量0.01％～1％的金属离子化合物，并将分散剂和金属离子化合物倒入球磨机内进行循环球磨和分散完成一次浆料的制备，同时确保一次球磨分散时间为0.5～2h；b. Weigh 0.1% to 0.5% of the weight of lithium cobaltate and 0.1% to 1% of metal ion compound by weight of lithium cobaltate, and pour the dispersant and metal ion compound into the ball mill. Cyclic ball milling and dispersion to complete the preparation of a slurry, while ensuring a ball mill dispersion time of 0.5 ~ 2h;
c.再称取100～200Kg的钴酸锂，加入球磨机内进行球磨和分散完成二次浆料的制备，确保二次球磨分散时间为1～2h；c. Weigh 100-200Kg of lithium cobaltate, add to the ball mill for ball milling and dispersion to complete the preparation of the secondary slurry, to ensure that the secondary ball mill dispersion time is 1 ~ 2h;
d.完成球磨分散后，将浆料通过砂浆泵打入真空干燥机内进行干燥，干燥温度为100～200℃，干燥时间为2～5h；d. After the ball mill is dispersed, the slurry is pumped into a vacuum dryer through a mortar pump for drying, the drying temperature is 100-200 ° C, and the drying time is 2-5 h;
e.步骤d中完成干燥的物料加入窑炉中进行二次烧结，确保二次烧结温度为600～900℃，二次烧结时间为5～20h；e. The dried material in step d is added to the kiln for secondary sintering to ensure that the secondary sintering temperature is 600-900 ° C, and the secondary sintering time is 5-20 h;
f.将步骤e中二次烧结后的物料进行过筛和除铁，得到所需材料。f. The second sintered material in step e is sieved and iron removed to obtain the desired material.
其中，所述步骤b中所述金属离子化合物选取氢氧化镁、氢氧化铝、氢氧化锆、氢氧化钛、氢氧化锰、氢氧化镍、氢氧化钒、氢氧化铈、氢氧化锡等的一种或多种；所述步骤b中分散剂选取聚乙烯醇、聚乙二醇、聚丙烯酰胺、聚丙烯酸等的一种或多种。Wherein, in the step b, the metal ion compound is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, titanium hydroxide, manganese hydroxide, nickel hydroxide, vanadium hydroxide, barium hydroxide, tin hydroxide, and the like. One or more of the dispersing agents in the step b are one or more selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyacrylic acid and the like.
下面以具体实施例对本发明进行阐述The present invention will be described below by way of specific embodiments.
实施例1Example 1
本发明所揭示的一种高电压钴酸锂正极材料的水系包覆方法，具体步骤为：The water system coating method of the high voltage lithium cobaltate cathode material disclosed by the invention has the following specific steps:
a.以100Kg钴酸锂重量为基准，称取重量为25Kg的纯水，打入球磨机内，完成后开启循环；a. weighing 100Kg of pure water based on the weight of 100Kg of lithium cobalt oxide, into the ball mill, after the completion of the cycle;
b.分别称取0.1Kg的聚乙烯醇粉末、0.2Kg的氢氧化铝粉末，将聚乙烯醇和氢氧化铝粉末先后倒入球磨机内进行循环球磨和分散完成一次浆料制备，控制球磨循环时间为1h；b. Weigh 0.1Kg of polyvinyl alcohol powder and 0.2Kg of aluminum hydroxide powder respectively, and pour the polyvinyl alcohol and aluminum hydroxide powder into the ball mill successively for cyclic ball milling and dispersion to complete the preparation of the slurry, and control the ball milling cycle time. 1h;
c.称取100Kg的钴酸锂，加入球磨机内进行球磨和分散完成二次浆料制备， 控制二次球磨1h；c. Weigh 100Kg of lithium cobaltate, add it to the ball mill for ball milling and dispersion to complete the preparation of the secondary slurry. Control the second ball mill for 1h;
d.将制备完成的二次浆料采用砂浆泵打入真空干燥机内进行干燥，干燥温度为100℃，干燥时间为3h；d. The prepared secondary slurry is driven into a vacuum dryer by a mortar pump for drying, the drying temperature is 100 ° C, and the drying time is 3 h;
e.干燥后的物料加入窑炉中进行二次烧结，二次烧结温度为850℃，二次烧结时间为10h；e. The dried material is added to the kiln for secondary sintering, the secondary sintering temperature is 850 ° C, and the secondary sintering time is 10 h;
f.二次烧结后的物料再进行过筛和除铁，得到所需材料。f. The material after secondary sintering is further sieved and iron removed to obtain the desired material.
实施例2Example 2
本发明所揭示的一种高电压钴酸锂正极材料的水系包覆方法，具体步骤为：The water system coating method of the high voltage lithium cobaltate cathode material disclosed by the invention has the following specific steps:
a.以200Kg钴酸锂重量为基准，称取钴酸锂重量的50Kg的纯水，打入球磨机内，完成后开启循环；a. Based on the weight of 200 Kg of lithium cobalt oxide, weigh 50 Kg of pure water by weight of lithium cobaltate, and drive into a ball mill to complete the cycle after completion;
b.分别称取0.4Kg的聚丙烯酸粉末、0.5Kg的氢氧化镁粉末，将聚丙烯酸和氢氧化镁粉末先后倒入球磨机内进行循环球磨和分散完成一次浆料制备，控制球磨循环时间为1h；b. Weigh 0.4Kg of polyacrylic acid powder and 0.5Kg of magnesium hydroxide powder respectively, and pour the polyacrylic acid and magnesium hydroxide powder into the ball mill successively for cyclic ball milling and dispersion to complete the preparation of the slurry, and control the ball milling cycle time to 1h. ;
c.称取200Kg的钴酸锂，加入球磨机内进行球磨和分散完成二次浆料制备，控制二次球磨2h；c. Weigh 200Kg of lithium cobaltate, add to the ball mill for ball milling and dispersion to complete the secondary slurry preparation, control the second ball milling for 2h;
d.将二次浆料采用砂浆泵打入真空干燥机内进行干燥，干燥时间温度为150℃，干燥时间为3h；d. The secondary slurry is driven into a vacuum dryer by a mortar pump for drying, the drying time is 150 ° C, and the drying time is 3 h;
e.干燥后的物料加入窑炉中进行二次烧结。二次烧结温度为800℃，二次烧结时间为12h。e. The dried material is added to the kiln for secondary sintering. The secondary sintering temperature was 800 ° C, and the secondary sintering time was 12 h.
f.二次烧结后的物料再进行过筛和除铁，得到所需材料。f. The material after secondary sintering is further sieved and iron removed to obtain the desired material.
实施例3Example 3
本发明所揭示的一种高电压钴酸锂正极材料的水系包覆方法，具体步骤为：The water system coating method of the high voltage lithium cobaltate cathode material disclosed by the invention has the following specific steps:
a.以150Kg钴酸锂重量为基准，称取钴酸锂重量的40Kg的纯水，打入球 磨机内，完成后开启循环；a. Based on the weight of 150Kg of lithium cobalt oxide, weigh 40Kg of pure water by weight of lithium cobaltate and hit the ball. Inside the mill, the cycle is turned on after completion;
b.分别称取0.5Kg的聚乙二醇粉末、0.2Kg的氢氧化镁粉末、0.2Kg的氢氧化铝粉末，将聚丙烯酸、氢氧化镁粉末和氢氧化铝粉末先后倒入球磨机内进行循环球磨和分散完成一次浆料制备，控制球磨循环时间为2h；b. Weigh 0.5Kg of polyethylene glycol powder, 0.2Kg of magnesium hydroxide powder, 0.2Kg of aluminum hydroxide powder, and pour polyacrylic acid, magnesium hydroxide powder and aluminum hydroxide powder into the ball mill for circulation. Ball milling and dispersion to complete a slurry preparation, control ball milling cycle time is 2h;
c.称取150Kg的钴酸锂，加入球磨机内进行球磨和分散完成二次浆料制备，控制二次球磨2h；c. Weigh 150Kg of lithium cobaltate, add to the ball mill for ball milling and dispersion to complete the secondary slurry preparation, control the second ball milling for 2h;
d.将二次浆料采用砂浆泵打入真空干燥机内进行干燥，干燥时间温度为180℃，干燥时间为2h；d. The secondary slurry is driven into a vacuum dryer by a mortar pump for drying, the drying time is 180 ° C, and the drying time is 2 h;
e.干燥后的物料加入窑炉中进行二次烧结。二次烧结温度为850℃，二次烧结时间为12h。e. The dried material is added to the kiln for secondary sintering. The secondary sintering temperature was 850 ° C, and the secondary sintering time was 12 h.
f.二次烧结后的物料再进行过筛和除铁，得到所需材料。f. The material after secondary sintering is further sieved and iron removed to obtain the desired material.
以上述第一实施例为例对其微观结构按下述方法进行测试：Taking the above first embodiment as an example, the microstructure thereof was tested as follows:
采用扫描电镜观察包覆后的钴酸锂成品的表面形貌，得到的微观形态如图1所示，从图1可以看出，包覆后的钴酸锂颗粒为单晶颗粒，无团聚，颗粒表面光滑。The surface morphology of the coated lithium cobalt oxide product was observed by scanning electron microscopy. The microscopic morphology obtained is shown in Fig. 1. It can be seen from Fig. 1 that the coated lithium cobaltate particles are single crystal particles without agglomeration. The surface of the particles is smooth.
采用能谱分析仪(EDS)对钴酸锂产品的颗粒表面进行元素表征，从EDS图谱可以看出，钴酸锂的各组成元素均匀分布，Al均匀的包覆在颗粒表面。The particle surface of the lithium cobaltate product was characterized by an energy spectrum analyzer (EDS). It can be seen from the EDS spectrum that the constituent elements of lithium cobaltate are uniformly distributed, and Al is uniformly coated on the surface of the particle.
采用X射线衍射仪(XRD)对包覆后的钴酸锂产品进行物相分析，得到的谱图如图2所示，包覆后的钴酸锂的XRD谱图与钴酸锂的标准谱图一一对应，说明钴酸锂的结晶性好，晶体结构良好，包覆后的钴酸锂晶相单一、完整，未有杂相产生。X-ray diffractometry (XRD) was used to analyze the phase of the coated lithium cobalt oxide product. The obtained spectrum is shown in Fig. 2. The XRD spectrum of the coated lithium cobalt oxide and the standard spectrum of lithium cobaltate The one-to-one correspondence shows that the lithium cobaltate has good crystallinity and good crystal structure, and the coated lithium cobalt oxide crystal phase is single and complete, and no impurity phase is generated.
上述材料的电化学性能按照下述方法进行测试：用实施例一合成的钴酸锂材料为正极活性物质，锂片为负极，组装成扣式实验电池，正极膜的组成为m(活 性物质)∶m(乙炔黑)∶m(PVDF)＝90∶5∶5，采用蓝电测试***进行测试，充放电电压为3～4.5V，分别在常温(25℃)和高温(45℃)环境下进行扣电测试。The electrochemical properties of the above materials were tested according to the following method: the lithium cobaltate material synthesized in Example 1 was used as the positive electrode active material, and the lithium plate was used as the negative electrode, and assembled into a button type experimental battery, and the composition of the positive electrode film was m (live Substance): m (acetylene black): m (PVDF) = 90:5:5, tested by blue electric test system, charge and discharge voltage is 3 ~ 4.5V, respectively at normal temperature (25 ° C) and high temperature (45 ° C The power-off test is carried out under the environment.
在0.1C的充放电条件下进行扣电测试，得到的首次充放电曲线如图4所示，25℃时，首次放电比容量可达到192.1mA·h/g，首次充放电效率93.1％；45℃时，首次放电比容量可达187.4mA·h/g，首次充放电效率94.3％，放电比容量较常规钴酸锂(3.0～4.3V)高30％左右。The charge-discharge test was carried out under the charge and discharge conditions of 0.1C, and the first charge-discharge curve obtained is shown in Fig. 4. At 25 °C, the first discharge specific capacity can reach 192.1 mA·h/g, and the first charge-discharge efficiency is 93.1%; At °C, the first discharge specific capacity can reach 187.4mA·h/g, the first charge and discharge efficiency is 94.3%, and the discharge specific capacity is about 30% higher than the conventional lithium cobaltate (3.0~4.3V).
分别在0.1C、0.2C、0.5C、0.8C、1C、2C和5C下进行倍率性能测试，得到的倍率性能如图5所示。25℃时，5C下的放电比容量可达到182.4mA·h/g，5C/0.1C的容量比为95.10％；45℃时，5C下的放电比容量可达到179.7mA·h/g，5C/0.1C的容量比为95.64％，本发明材料的倍率性能优良。The rate performance tests were carried out at 0.1 C, 0.2 C, 0.5 C, 0.8 C, 1 C, 2 C and 5 C, respectively, and the obtained rate performance is shown in FIG. 5 . At 25 °C, the specific discharge capacity at 5C can reach 182.4mA·h/g, and the capacity ratio of 5C/0.1C is 95.10%. At 45°C, the specific discharge capacity at 5C can reach 179.7mA·h/g, 5C. The capacity ratio of /0.1 C is 95.64%, and the material of the present invention has excellent rate performance.
以1C/1C充放电倍率在3.0～4.5V的电压范围内进行循环测试，得到的循环测试图如图6所示。25℃时，100次循环后容量保持率为94.5％；45℃时，100次循环后容量保持率为90.4％。本发明材料在常温和高温下的倍率性能优良。The cycle test was carried out in a voltage range of 3.0 to 4.5 V at a charge/discharge rate of 1 C/1 C, and the obtained cycle test chart is shown in Fig. 6. At 25 ° C, the capacity retention rate after 94 cycles was 94.5%; at 45 ° C, the capacity retention after 100 cycles was 90.4%. The material of the present invention is excellent in rate performance at normal temperature and high temperature.
本发明的技术内容及技术特征已揭示如上，然而熟悉本领域的技术人员仍可能基于本发明的教示及揭示而作种种不背离本发明精神的替换及修饰，因此，本发明保护范围应不限于实施例所揭示的内容，而应包括各种不背离本发明的替换及修饰，并为本专利申请权利要求所涵盖 The technical content and the technical features of the present invention have been disclosed as above, but those skilled in the art can still make various alternatives and modifications without departing from the spirit and scope of the present invention based on the teachings and disclosures of the present invention. Therefore, the scope of protection of the present invention should not be limited to The disclosure of the embodiments should include various alternatives and modifications without departing from the invention, and is covered by the claims of the present application.

Claims (3)

  1. 一种高电压钴酸锂正极材料的水系包覆方法，其特征在于：包括以下工艺步骤：An aqueous coating method for a high voltage lithium cobaltate cathode material, comprising: the following process steps:
    a.以钴酸锂重量为基准，称取钴酸锂重量20％～40％的纯水，打入球磨机内球磨，完成后开启循环；a. based on the weight of lithium cobalt oxide, weigh 20% to 40% of the weight of lithium cobaltate, and enter the ball mill in the ball mill, after the completion of the cycle;
    b.分别称取占钴酸锂重量的0.1％～0.5％的分散剂和金属离子占钴酸锂重量0.01％～1％的金属离子化合物，并将分散剂和金属离子化合物倒入球磨机内进行循环球磨和分散完成一次浆料的制备，并确保一次球磨分散时间为0.5～2h；b. Weigh 0.1% to 0.5% of the weight of lithium cobaltate and 0.1% to 1% of metal ion compound by weight of lithium cobaltate, and pour the dispersant and metal ion compound into the ball mill. Cyclic ball milling and dispersion to complete the preparation of a slurry, and to ensure a ball mill dispersion time of 0.5 ~ 2h;
    c.再称取100～200Kg的钴酸锂，加入球磨机内进行球磨和分散完成二次浆料的制备，确保二次球磨分散时间为1～2h；c. Weigh 100-200Kg of lithium cobaltate, add to the ball mill for ball milling and dispersion to complete the preparation of the secondary slurry, to ensure that the secondary ball mill dispersion time is 1 ~ 2h;
    d.完成球磨分散后，将浆料通过砂浆泵打入真空干燥机内进行干燥，干燥温度为100～200℃，干燥时间为2～5h；d. After the ball mill is dispersed, the slurry is pumped into a vacuum dryer through a mortar pump for drying, the drying temperature is 100-200 ° C, and the drying time is 2-5 h;
    e.步骤d中完成干燥的物料加入窑炉中进行二次烧结，确保二次烧结温度为600～900℃，二次烧结时间为5～20h；e. The dried material in step d is added to the kiln for secondary sintering to ensure that the secondary sintering temperature is 600-900 ° C, and the secondary sintering time is 5-20 h;
    f.将步骤e中二次烧结后的物料进行过筛和除铁，得到所需材料。f. The second sintered material in step e is sieved and iron removed to obtain the desired material.
  2. 根据权利要求1所述的制备方法，其特征在于：所述步骤b中所述金属离子化合物选取氢氧化镁、氢氧化铝、氢氧化锆、氢氧化钛、氢氧化锰、氢氧化镍、氢氧化钒、氢氧化铈、氢氧化锡中的一种或多种。The preparation method according to claim 1, wherein the metal ion compound in the step b is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, titanium hydroxide, manganese hydroxide, nickel hydroxide and hydrogen. One or more of vanadium oxide, barium hydroxide, and tin hydroxide.
  3. 根据权利要求1所述的制备方法，其特征在于：所述步骤b中分散剂选取聚乙烯醇、聚乙二醇、聚丙烯酰胺、聚丙烯酸中的一种或多种。 The preparation method according to claim 1, wherein the dispersing agent in the step b is one or more selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylamide, and polyacrylic acid.
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