WO2016188477A2 - 碳包覆三元正极材料及其制备方法、锂离子电池 - Google Patents

碳包覆三元正极材料及其制备方法、锂离子电池 Download PDF

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WO2016188477A2
WO2016188477A2 PCT/CN2016/083632 CN2016083632W WO2016188477A2 WO 2016188477 A2 WO2016188477 A2 WO 2016188477A2 CN 2016083632 W CN2016083632 W CN 2016083632W WO 2016188477 A2 WO2016188477 A2 WO 2016188477A2
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positive electrode
electrode material
ternary positive
carbon
coated
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French (fr)
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WO2016188477A3 (zh
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褚晓东
何建福
李宝华
贺艳兵
刘玉秀
杜鸿达
康飞宇
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清华大学深圳研究生院
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Definitions

  • the invention relates to a preparation method of a carbon-coated ternary positive electrode material and a carbon-coated ternary positive electrode material and a lithium ion battery containing the carbon-coated ternary positive electrode material.
  • Lithium-ion batteries are widely used in life, such as laptops, cell phones, digital cameras, and electric vehicles.
  • the positive electrode material plays an important role in the performance of the battery.
  • the ternary cathode material LiNi 1-xy Co x Mn y O 2 has obvious ternary synergistic effect, forming a three-phase solid solution system of LiCoO 2 /LiNiO 2 /LiMnO 2 , which takes into account LiCoO 2 , LiNiO 2 and LiMnO 2
  • the advantages of the three materials while to a certain extent, make up for the shortcomings of the three materials.
  • LiNi 1-xy Co x Mn y O 2 Compared with LiNiO2 and LiMnO 2 , LiNi 1-xy Co x Mn y O 2 has good stability and is easy to prepare. LiNi 1-xy Co x Mn y O 2 is less prone to Jahn-Teller distortion than spinel LiMn 2 O 4 ; LiNi 1-xy Co x Mn y O 2 has a higher voltage platform than LiFePO 4 High conductivity, high tap density and so on.
  • the industrial synthesis of ternary cathode materials is mainly through high temperature solid phase method.
  • the high-temperature solid-phase method is simple in process and convenient in control. It is the main preparation method currently used in industrialization.
  • high temperature consumes a lot of energy during the preparation process, the reaction materials are mixed unevenly, and the particle size is difficult to control, resulting in poor performance between batches. Uniform problem.
  • the carbon-coated ternary cathode material is used to increase the conductivity of the material, and the material's rate charge and discharge performance is optimized.
  • the particulate conductive carbon and the particulate positive electrode material are mechanically ground and mixed.
  • This mixing method has defects in poor contact between the carbon and the positive electrode material, so that the electrons cannot smoothly migrate. Affects the rate performance of the material, and ball milling increases process time and energy consumption.
  • the preparation of non-mechanically mixed carbon-coated ternary cathode materials in the prior art is often complicated.
  • a preparation method of a carbon-coated ternary positive electrode material wherein the chemical formula of the ternary positive electrode material is LiNi 1-xy Co x Mn y O 2 , wherein 0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 0.3, the preparation method comprises the following Step: preparing nickel-cobalt-manganese coprecipitate as a ternary positive electrode material precursor by using nickel salt, cobalt salt and manganese salt as raw materials; preparing a suspension of the above ternary positive electrode material precursor, in the suspension The mass percentage concentration of the ternary positive electrode material precursor is 5% to 30%; and the molar ratio of Li:(Ni+Co+Mn) is 1.03 to 1.05:1 is added to the suspension of the ternary positive electrode material precursor.
  • Lithium acrylate adding ammonium persulfate to the suspension of the ternary positive electrode material precursor to which lithium acrylate is added at a temperature of 50 ° C to 80 ° C to polymerize lithium acrylate to form lithium polyacrylate and coating the lithium acrylate
  • the ternary positive electrode material precursor particles thereby obtaining a suspension of the lithium acrylate-coated ternary positive electrode material precursor, the mass of the ammonium persulfate is 2% to 10% of the mass of the lithium acrylate, and the reaction time is 5 ⁇ 8 hours; a suspension of the above-mentioned polyacrylic acid lithium coated ternary positive electrode material precursor Line dried to give lithium polyacrylate coated spherical ternary positive electrode material precursor particles; as well as ternary positive electrode material of a lithium precursor particles described above coated sintered polyacrylic acid, to give a positive electrode material coated with carbon three yuan.
  • a carbon-coated ternary positive electrode material prepared by the preparation method as described above.
  • a lithium ion battery comprising a positive electrode comprising a carbon-coated ternary positive electrode material prepared by the preparation method as described above.
  • lithium polyacrylate is simultaneously used as a lithium source and a carbon source, and a ternary positive electrode material is obtained during sintering while the ternary positive electrode material is coated with carbon to prevent ternary positive electrode.
  • the material particles grow excessively, and a large number of pores are formed on the carbon-coated ternary positive electrode material, which greatly increases the specific surface area of the carbon-coated ternary positive electrode material, thereby improving the electrochemical performance of the carbon-coated ternary positive electrode material. Sex.
  • the preparation is simple, no ball milling is required, and energy consumption is reduced.
  • the carbon-coated ternary positive electrode material does not generate impurities during the production process, and is environmentally friendly and saves the disposal cost of waste liquid or waste residue.
  • Example 1 is an XRD chart of a carbon-coated ternary positive electrode material prepared in Example 1 of the present invention.
  • Example 2 is an SEM image showing a 10,000-fold magnification of a carbon-coated ternary positive electrode material prepared in Example 1 of the present invention.
  • Example 3 is an SEM image of a carbon-coated ternary positive electrode material prepared in Example 1 of the present invention at a magnification of 50,000 times.
  • Example 4 is a TEM image of a carbon-coated ternary positive electrode material prepared in Example 1 of the present invention.
  • Example 5 is a cycle performance curve of a carbon-coated ternary positive electrode material prepared in Example 1 of the present invention.
  • Example 6 is a graph showing the rate charge and discharge performance of the carbon-coated ternary positive electrode material prepared in Example 1 of the present invention.
  • the invention provides a preparation method of a carbon-coated ternary positive electrode material applied to a positive electrode of a lithium ion battery, wherein the ternary positive electrode material is lithium nickel cobalt manganese oxide, and the chemical formula thereof is LiNi 1-xy Co x Mn y O 2 . Where 0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 0.3, the preparation method comprises the following steps:
  • step S1 nickel-cobalt-manganese coprecipitate Ni 1-xy Co x Mn y (OH) 2 is prepared as a ternary positive electrode material precursor by using nickel salt, cobalt salt and manganese salt as raw materials.
  • step S2 a suspension of the precursor of the ternary positive electrode material is prepared, wherein the mass percentage concentration of the ternary positive electrode material precursor in the suspension is 5% to 30%.
  • the precursor content of the ternary positive electrode material in the suspension is less than 5%, the yield of the prepared carbon-coated ternary positive electrode material is lower, thereby affecting economic benefits; and above 30%, excessive precursor content will affect Subsequent drying effect.
  • step S3 lithium acrylate is added to the suspension of the ternary positive electrode material precursor in a molar ratio of Li:(Ni+Co+Mn) of 1.03 to 1.05:1, and the mixture is stirred and mixed. Since a part of lithium is lost in the subsequent sintering process, the molar ratio of added Li to (Ni + Co + Mn) is slightly larger than 1; however, the molar ratio of Li to (Ni + Co + Mn) is preferably not more than 1.05: 1, to avoid excessive lithium content affects the electrochemical properties of the finally produced carbon-coated ternary cathode material.
  • step S4 ammonium persulfate is added as a polymerization initiator for lithium acrylate to the suspension of the ternary positive electrode material precursor to which lithium acrylate is added at a temperature of 50 ° C to 80 ° C, and stirred to make lithium acrylate
  • the polymerization reaction generates lithium polyacrylate and simultaneously coats the precursor particles of the ternary positive electrode material to obtain a suspension of a lithium acrylate-coated ternary positive electrode material precursor.
  • the mass of ammonium persulfate is 2% to 10% of the mass of lithium acrylate, and the reaction time is 5 to 8 hours.
  • step S5 the suspension of the lithium acrylate-coated ternary positive electrode material precursor is dried to obtain a spherical polyacrylic acid-coated ternary positive electrode material precursor particle.
  • step S6 the polyacrylic acid lithium coated ternary positive electrode material precursor particles are sintered to obtain the carbon coated ternary positive electrode material.
  • lithium in the lithium polyacrylate is uniformly diffused in the ternary positive electrode material precursor to obtain the ternary positive electrode material LiNi 1-xy Co x Mn y O 2 ; and the carbon in the polyacrylic acid lithium is coated in the third The outside of the positive electrode material particles finally obtains the carbon-coated ternary positive electrode material.
  • a metal salt aqueous solution wherein 0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 0.3, the concentration of the aqueous metal salt solution is 0.01 mol/L to 1 mol/L; a surfactant is added to the aqueous metal salt solution, wherein the surfactant
  • the mass is 1% to 10% of the mass of Ni 1-xy Co x Mn y (OH) 2 synthesized from the aqueous metal salt solution; at a temperature of 25 ° C to 50 ° C and under inert gas protection, the peristaltic pump will
  • the sodium hydroxide solution and the ammonia water may be first mixed to prepare a mixed solution, and then the aqueous solution of the surfactant-added metal salt and the mixed solution are slowly added to the reaction vessel by a peristaltic pump to react.
  • the concentration of sodium hydroxide is 0.02 mol/L to 2 mol/L
  • the concentration of ammonia water is twice the concentration of sodium hydroxide.
  • the nickel salt may be selected from one or more of nickel sulfate, nickel acetate, and nickel nitrate.
  • the cobalt salt may be selected from one or more of cobalt sulfate, cobalt acetate, and cobalt nitrate.
  • the manganese salt may be selected from one or more of manganese sulfate, manganese acetate, and manganese nitrate.
  • the surfactant may be selected from one or more of polyvinylpyrrolidone, polyethylene glycol, and cetyltrimethylammonium chloride.
  • the reaction vessel When the aqueous solution of the surfactant-added metal salt, the sodium hydroxide solution and the aqueous ammonia solution are slowly added to the reaction vessel by the peristaltic pump, the reaction vessel may be ultrasonically shaken to make the solution uniformly mixed and the precipitated particles are made. The size is more uniform. Among them, the frequency of the ultrasonic wave can be 30KHz ⁇ 100KHz.
  • lithium polyacrylate is formed by in-situ polymerization of lithium acrylate to simultaneously coat the ternary positive electrode material precursor particles, so that the polyacrylic acid lithium coating is more uniform, that is, the subsequent carbon coating is three.
  • the carbon in the positive electrode material is also more uniformly coated.
  • the drying method is spray drying. Drying of the suspension of the lithium acrylate-coated ternary positive electrode material precursor by spray drying is advantageous for improving efficiency.
  • the spray drying causes the polyacrylic acid lithium-coated ternary positive electrode material precursor in the suspension of the lithium acrylate-coated ternary positive electrode material precursor to be uniformly agglomerated to obtain a more uniform and spherical particle size.
  • the lithium acrylate-coated ternary positive electrode material precursor secondary particles, so that the secondary particles of the carbon-coated ternary positive electrode material obtained by subsequent sintering are spherical and the secondary particles have a more uniform particle size.
  • step S6 of the embodiment the precursor particles of the ternary positive electrode material coated with polyacrylic acid lithium are pre-fired for 3 to 12 hours under inert gas and at a temperature of 300 ° C to 500 ° C, and then in air at 700 ° C. Sintering at 1000 ° C for 12 to 24 hours, thereby obtaining a carbon-coated ternary positive electrode material.
  • step S6 the precursor particles of the ternary positive electrode material coated with polyacrylic acid lithium are first sintered at an inert gas and at a lower temperature to obtain carbon and hard-coated with the ternary positive electrode material to prevent excessive growth of the ternary positive electrode material particles, and at the same time, Sintering at a lower temperature ensures that lithium diffuses uniformly in the precursor of the ternary positive electrode material; and subsequent sintering at a higher temperature in the air causes oxidation of nickel, cobalt and manganese in the precursor of the ternary positive electrode material, and at the same time, low temperature
  • the sintered carbon is partially decomposed at a high temperature, leaving a large number of pores on the particles, which greatly increases the specific surface area of the carbon-coated ternary cathode material, thereby improving the electrochemical properties of the carbon-coated ternary cathode material.
  • the carbon-coated ternary positive electrode material obtained in the step S6 is a secondary particle.
  • the carbon-coated ternary positive electrode material has a simple preparation method and does not require ball milling, thereby reducing energy consumption.
  • the carbon-coated ternary positive electrode material does not generate impurities during the production process, and does not require an impurity removal step, simplifies the production process, is environmentally friendly, and saves the disposal cost of waste liquid or waste residue.
  • the lithium polyacrylate coated with the ternary positive electrode material precursor obtained after the polymerization reaction of the above step S4 can further agglomerate between the ternary positive electrode material precursor particles. Lithium polyacrylate is simultaneously used as a lithium source and a carbon source.
  • the ternary cathode material is obtained by sintering in the above step S6, and the ternary cathode material is coated with carbon, which can suppress the agglomeration between the primary particles of the ternary cathode material to some extent.
  • the carbon-coated ternary positive electrode material prepared by the above method has a primary particle diameter of several hundred nanometers, a secondary particle diameter of several micrometers, a regular shape, good dispersibility, and uniform particle size distribution.
  • the carbon which is partially decomposed when the carbon coated with the ternary positive electrode material is sintered at a higher temperature is beneficial to the entry of the electrolyte in the battery, so as to increase the contact area between the ternary positive electrode material and the electrolyte to strengthen the battery.
  • the carbon-coated ternary positive electrode material prepared by the above method has a larger specific surface area of the secondary particles, which is advantageous for improving the cycle life and rate performance of the battery using the carbon-coated ternary positive electrode material.
  • Polyvinylpyrrolidone was added to the above aqueous metal salt solution and stirred until completely dissolved.
  • the mass of the polyvinylpyrrolidone is 1% of the mass of Ni 1-xy Co x Mn y (OH) 2 synthesized from the aqueous metal salt solution.
  • a mixed solution of 300 mL of sodium hydroxide and ammonia water was prepared.
  • the concentration of sodium hydroxide in the mixed solution was 0.02 mol/L, and the concentration of aqueous ammonia was 0.04 mol/L.
  • the above ternary positive electrode material precursor was formulated into a suspension of 200 mL of a ternary positive electrode material precursor, wherein the suspension had a mass percentage concentration of 8% of the ternary positive electrode material precursor.
  • the mass of ammonium persulfate is 2% of the mass of lithium acrylate, and the reaction time is 8 hours.
  • the suspension of the above-mentioned polyacrylic acid lithium-coated ternary positive electrode material precursor was spray-dried to obtain spherical lithium acrylate-coated ternary positive electrode material precursor particles.
  • the above-mentioned polyacrylic acid lithium-coated ternary positive electrode material precursor particles were sintered under argon gas at 400 ° C for 3 hours, and then sintered under air at 700 ° C for 12 hours to obtain a carbon-coated ternary positive electrode material. .
  • Example 1 is an XRD spectrum of the carbon-coated ternary positive electrode material prepared in Example 1. As can be seen from FIG. 1, the material composition obtained in Example 1 is a carbon-coated ternary positive electrode material, and its pattern is consistent with the standard pattern of the carbon-coated ternary positive electrode material.
  • Example 2 is a SEM photograph of a carbon-coated ternary positive electrode material prepared in Example 1 at a magnification of 10,000 times.
  • the carbon-coated ternary positive electrode material has a spherical shape and a particle size of 5 ⁇ m. 10 ⁇ m.
  • FIG. 3 is a SEM photograph of a carbon-coated ternary positive electrode material prepared in Example 1 at a magnification of 50,000 times.
  • FIG. 3 shows that the carbon-coated ternary positive electrode material has a primary particle diameter of 200 nm to 300 nm, and the shape is regular. Flaky.
  • Example 4 is a transmission electron micrograph of the primary particles of the carbon-coated ternary positive electrode material prepared in Example 1, wherein the material layer between the two arrows is a carbon coating layer, and the thickness of the carbon coating layer is about 5 nm.
  • Example 5 is a graph showing the cycle performance of a carbon-coated ternary positive electrode material prepared in Example 1 as a positive electrode of a lithium ion battery. It can be seen that the specific specific discharge capacities of the carbon-coated ternary positive electrode materials prepared in Example 1 at 0.2C, 1C, 2C, 5C, and 10C are 168 mAh/g, 148.3 mAh/g, and 135.6 mAh/g, respectively. 120mAh/g, 95.2mAh/g, the specific capacity is still maintained at about 160mAh/g after being cycled at 0.2C after the rate cycle, indicating that the carbon coated ternary positive electrode material prepared in Example 1 has better cycle performance. .
  • Example 6 is a graph showing the rate charge and discharge performance of the carbon-coated ternary positive electrode material prepared in Example 1 as a positive electrode of a lithium ion battery. It can be seen that the carbon-coated ternary positive electrode material prepared in Example 1 is at normal temperature and pressure. When the charge and discharge cycle was performed with a current of 1 C, the first discharge capacity was 145.7 mAh/g, the discharge capacity after 100 cycles was 131.7 mAh/g, and the capacity retention rate was 90.2%, which was described in Example 1. The carbon coated ternary positive electrode material has better rate performance. The carbon-coated ternary positive electrode material prepared in Example 1 has good electrochemical properties.
  • Polyvinylpyrrolidone was added to the above aqueous metal salt solution and stirred until completely dissolved.
  • the mass of the polyvinylpyrrolidone is 3% of the mass of Ni 1-xy Co x Mn y (OH) 2 synthesized from the aqueous metal salt solution.
  • a mixed solution of 300 mL of sodium hydroxide and ammonia water was prepared.
  • the concentration of sodium hydroxide in the mixed solution was 2 mol/L, and the concentration of ammonia water was 4 mol/L.
  • the above ternary positive electrode material precursor was formulated into a suspension of 200 mL of a ternary positive electrode material precursor, wherein the suspension had a mass percentage concentration of 8% of the ternary positive electrode material precursor.
  • the mass of ammonium persulfate is 5% by mass of lithium acrylate, and the reaction time is 8 hours.
  • the suspension of the above-mentioned polyacrylic acid lithium-coated ternary positive electrode material precursor was spray-dried to obtain spherical lithium acrylate-coated ternary positive electrode material precursor particles.
  • the above-mentioned polyacrylic acid lithium-coated ternary positive electrode material precursor particles were sintered under argon gas and 500 ° C for 6 hours, and then sintered under air and 1000 ° C for 20 hours to obtain a carbon-coated ternary positive electrode material. .

Abstract

一种碳包覆三元正极材料的制备方法，其步骤如下：制备三元正极材料前驱体；制备该三元正极材料前驱体的悬浊液，该悬浊液中该三元正极材料前驱体的质量百分比浓度为5%~30%；按Li:（Ni+Co+Mn）为1.03~1.05:1的摩尔比往该三元正极材料前驱体的悬浊液中加入丙烯酸锂；在50℃~80℃的温度下往该带丙烯酸锂的三元正极材料前驱体的悬浊液中加入过硫酸铵，以使丙烯酸锂进行聚合反应从而得到聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液，该过硫酸铵的质量为该丙烯酸锂质量的2%~10%，反应时间为5~8小时；对该聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液进行干燥，得到球状颗粒；以及对该聚丙烯酸锂包覆的三元正极材料前驱体颗粒进行烧结，得到碳包覆三元正极材料。

Description

碳包覆三元正极材料及其制备方法、锂离子电池 技术领域
本发明涉及一种碳包覆三元正极材料的制备方法及制得的碳包覆三元正极材料及含有该碳包覆三元正极材料的锂离子电池。
背景技术
锂离子电池被广泛地运用于生活中，例如笔记本电脑、手机、数码相机及电动车等。而正极材料作为电池的组成部分，对电池的性能起着重要作用。目前，三元正极材料LiNi1-x-yCoxMnyO2具有明显的三元协同效应，形成了LiCoO2/LiNiO2/LiMnO2三相的固溶体系，它兼顾LiCoO2、LiNiO2及LiMnO2三种材料的优点，同时在一定的程度上弥补三种材料各自的不足。与LiNiO2和LiMnO2相比，LiNi1-x-yCoxMnyO2稳定性好、容易制备。与尖晶石LiMn2O4相比，LiNi1-x-yCoxMnyO2不易发生Jahn-Teller畸变效应；与LiFePO4相比，LiNi1-x-yCoxMnyO2具有电压平台高、电导率高、振实密度大等优点。
目前，三元正极材料的工业合成主要通过高温固相法。高温固相法过程简单，控制方便，是目前工业化中主要采用的制备方法，但制备过程中高温消耗大量能源，反应材料混合不均，颗粒尺寸难以控制，造成了每批次产品之间性能不均一的问题。为了更好发挥三元正极材料的性能，通常会对其进行改性。例如，通过碳包覆三元正极材料来提高材料的导电系数，优化材料的倍率充放电性能。然而，现有的电池制作过程中往往是将颗粒型的导电碳和颗粒型的正极材料机械地球磨混合，这种混合方式存在碳与正极材料接触不良的缺陷，从而使得电子不能顺畅的迁移，影响材料的倍率性能，且球磨增加了制程时间和能耗。而现有技术中非机械混合的碳包覆三元正极材料的制备往往比较复杂。
发明内容
鉴于上述情况，有必要提供一种通过丙烯酸锂原位聚合以实现碳包覆的、制备简单、能耗低且环保的碳包覆三元正极材料的制备方法。
另外，还有必要提供一种上述方法制备的碳包覆三元正极材料及应用该碳包覆三元正极材料的电池。
一种碳包覆三元正极材料的制备方法，该三元正极材料的化学式为LiNi1-x-yCoxMnyO2，其中0<x≤0.4，0<y≤0.3，该制备方法包括如下步骤：以镍盐、钴盐、锰盐为原料，反应制备镍钴锰的共沉淀物作为三元正极材料前驱体；制备上述三元正极材料前驱体的悬浊液，该悬浊液中该三元正极材料前驱体的质量百分比浓度为5%~30%；按Li:（Ni+Co+Mn）为1.03~1.05:1的摩尔比往该三元正极材料前驱体的悬浊液中加入丙烯酸锂；在50℃~80℃的温度下往该加有丙烯酸锂的三元正极材料前驱体的悬浊液中加入过硫酸铵，以使丙烯酸锂进行聚合反应生成聚丙烯酸锂并包覆该三元正极材料前驱体颗粒，从而得到聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液，该过硫酸铵的质量为该丙烯酸锂质量的2%~10%，反应时间为5~8小时；对上述聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液进行干燥，得到球状聚丙烯酸锂包覆的三元正极材料前驱体颗粒；以及对上述聚丙烯酸锂包覆的三元正极材料前驱体颗粒进行烧结，得到碳包覆三元正极材料。
一种如上所述制备方法制备的碳包覆三元正极材料。
一种锂离子电池，包括正极，该正极包括如上所述制备方法制备的碳包覆三元正极材料。
本发明的碳包覆三元正极材料的制备方法中，聚丙烯酸锂同时作为锂源及碳源，在烧结时得到三元正极材料同时该三元正极材料被碳包覆，以防止三元正极材料颗粒过度长大，且包覆碳的三元正极材料上形成大量的孔道，极大的提高了碳包覆三元正极材料的比表面积，从而提高了碳包覆三元正极材料的电化学性。另外，该制备简单，不需进行球磨，进而降低了能耗。该碳包覆三元正极材料在制作过程并未产生杂质，比较环保且节省废液或废渣的处理成本。
 附图说明
图1为本发明实施例1制备的碳包覆三元正极材料的XRD图。
图2为本发明实施例1制备的碳包覆三元正极材料放大10000倍的SEM图。
图3为本发明实施例1制备的碳包覆三元正极材料放大50000倍的SEM图。
图4为本发明实施例1制备的碳包覆三元正极材料的TEM图。
图5为本发明实施例1制备的碳包覆三元正极材料的循环性能曲线。
图6为本发明实施例1制备的碳包覆三元正极材料的倍率充放电性能曲线。
具体实施方式
本发明提供一种应用于锂离子电池正极中的碳包覆三元正极材料的制备方法，该三元正极材料为镍钴锰酸锂，其化学式为LiNi1-x-yCoxMnyO2，其中0<x≤0.4，0<y≤0.3，该制备方法包括如下步骤：
步骤S1，以镍盐、钴盐、锰盐为原料，反应制备镍钴锰的共沉淀物Ni1-x-yCoxMny(OH)2作为三元正极材料前驱体。
步骤S2，制备上述三元正极材料前驱体的悬浊液，其中，该悬浊液中三元正极材料前驱体的质量百分比浓度为5%~30%。悬浊液中三元正极材料前驱体含量低于5%时，制备的碳包覆三元正极材料的产量较低，从而影响经济效益；而高于30%时，前驱体含量过多将影响后续的干燥效果。
步骤S3，按Li:（Ni+Co+Mn）为1.03~1.05:1的摩尔比往所述三元正极材料前驱体的悬浊液中加入丙烯酸锂并搅拌混合。由于在后续的烧结过程中会损失部分锂，因此加入的Li与（Ni+Co+Mn）的摩尔比值稍大于1；但是Li与（Ni+Co+Mn）的摩尔比值最好不要大于1.05:1，以避免锂含量过多影响最终制得的碳包覆三元正极材料的电化学性能。
步骤S4，在50℃~80℃的温度下往上述加有丙烯酸锂的三元正极材料前驱体的悬浊液中加入过硫酸铵作为丙烯酸锂聚合的引发剂，并搅拌以使丙烯酸锂进行原位聚合反应生成聚丙烯酸锂同时包覆该三元正极材料前驱体颗粒，从而得到聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液。其中，过硫酸铵的质量为丙烯酸锂质量的2%~10%，反应时间为5~8小时。
步骤S5，对上述聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液进行干燥，得到球状聚丙烯酸锂包覆的三元正极材料前驱体颗粒。
步骤S6，对上述聚丙烯酸锂包覆的三元正极材料前驱体颗粒进行烧结，得到所述碳包覆三元正极材料。烧结过程中，聚丙烯酸锂中的锂在三元正极材料前驱体中扩散均匀得到所述三元正极材料LiNi1-x-yCoxMnyO2；而聚丙烯酸锂中的碳则包覆在三元正极材料颗粒的外部，最终得到所述碳包覆三元正极材料。
本实施方式的步骤S1中，制备三元正极材料前驱体的具体步骤如下：将镍盐、钴盐、锰盐按照Ni:Co:Mn=(1-x-y):x:y的摩尔比配制成金属盐水溶液，其中，0<x≤0.4，0<y≤0.3，该金属盐水溶液的浓度为0.01mol/L~1mol/L；往金属盐水溶液中加入表面活性剂，其中，表面活性剂的质量为可由该金属盐水溶液合成的Ni1-x-yCoxMny(OH)2的质量的1%~10%；在25℃~50℃的温度及惰性气体保护的条件下，通过蠕动泵将加有表面活性剂的金属盐水溶液、氢氧化钠溶液及氨水同时缓慢加入反应容器中反应从而得到镍钴锰的共沉淀物，其中，各组分的摩尔比为（Ni2++Co2++Mn2+）:OH-:NH4 +=1:2:2，反应时间为2~12小时；用去离子水或乙醇清洗沉淀物，从而得到三元正极材料前驱体。在其它实施方式中，可先将氢氧化钠溶液和氨水混合配制成混合溶液，然后再通过蠕动泵将加有表面活性剂的金属盐水溶液以及该混合溶液同时缓慢加入反应容器中反应。该混合溶液中，氢氧化钠的浓度为0.02mol/L~2mol/L，氨水的浓度为氢氧化钠浓度的两倍。
该镍盐可选自硫酸镍、醋酸镍及硝酸镍中的一种或几种。该钴盐可选自硫酸钴、醋酸钴及硝酸钴中的一种或几种。该锰盐可选自硫酸锰、醋酸锰及硝酸锰中的一种或几种。
该表面活性剂可选自聚乙烯吡咯烷酮、聚乙二醇及十六烷基三甲基氯化铵中的一种或几种。
所述通过蠕动泵将加有表面活性剂的金属盐水溶液、氢氧化钠溶液及氨水溶液同时缓慢加入反应容器时，可对该反应容器进行超声震荡，以使得溶液混合均匀且使得沉淀物的颗粒大小较为均匀。其中，超声波的频率可为30KHz~100KHz。
本实施方式的步骤S4中，通过丙烯酸锂的原位聚合反应生成聚丙烯酸锂同时包覆该三元正极材料前驱体颗粒，可使得聚丙烯酸锂包覆的更加均匀，即后续的碳包覆三元正极材料中碳也包覆的更加均匀。
本实施方式的步骤S5中，该干燥方法为喷雾干燥。使用喷雾干燥对聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液进行干燥，有利于提高效率。另外，喷雾干燥使得聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液中的聚丙烯酸锂包覆的三元正极材料前驱体较均匀地团聚从而得到粒径更均匀且呈球状的聚丙烯酸锂包覆的三元正极材料前驱体二次颗粒，从而使得后续烧结得到的碳包覆三元正极材料的二次颗粒呈球状且该二次颗粒的粒径更均匀。
本实施方式的步骤S6中，将聚丙烯酸锂包覆的三元正极材料前驱体颗粒先在惰性气体及300℃~500℃的温度条件下预烧3~12小时，而后在空气及700℃~1000℃的条件下烧结12~24小时，从而得到碳包覆三元正极材料。步骤S6中聚丙烯酸锂包覆的三元正极材料前驱体颗粒先在惰性气体及较低温下烧结得到碳并硬化包覆三元正极材料，以防止三元正极材料颗粒过度长大，同时，在较低温度下烧结可保证锂在三元正极材料前驱体中扩散均匀；而后续再在空气中进行较高温度的烧结使得三元正极材料前驱体中的镍、钴、锰氧化，同时，低温下烧结的碳在高温下部分分解，在颗粒上留下大量孔道，极大的提高了碳包覆三元正极材料的比表面积，从而提高了碳包覆三元正极材料的电化学性。步骤S6得到的碳包覆三元正极材料为二次颗粒。
上述碳包覆三元正极材料的制备方法简单，不需进行球磨，进而降低了能耗。该碳包覆三元正极材料在制作过程并未产生杂质，无需除杂质步骤，简化制作流程，比较环保且节省废液或废渣的处理成本。在上述步骤S4的聚合反应后得到的包覆三元正极材料前驱体的聚丙烯酸锂可降低三元正极材料前驱体颗粒之间进一步团聚。聚丙烯酸锂同时作为锂源及碳源，在上述步骤S6的烧结得到三元正极材料同时该三元正极材料被碳包覆，其能够在一定程度上抑制三元正极材料一次颗粒间的团聚现象。上述方法制备的碳包覆三元正极材料，其一次颗粒的粒径为数百纳米，其二次颗粒的粒径为数微米，形状规则，分散性好，且粒度分布均匀。另外，包覆三元正极材料的碳在较高温度烧结时部分分解形成的孔道，有利于电池中电解液的进入，以增加三元正极材料与电解液之间的接触面积从而加强电池的电化学性能。上述方法制备的碳包覆三元正极材料的二次颗粒比表面积较大，有利于提高使用该碳包覆三元正极材料的电池的循环寿命和倍率性能。
实施例1
将硫酸镍、硫酸钴、硫酸锰按照Ni:Co:Mn=1:1:1的摩尔比与水混合配制300mL浓度为0.01mol/L的金属盐水溶液。
往上述金属盐水溶液中加入聚乙烯吡咯烷酮并搅拌直至完全溶解。其中，聚乙烯吡咯烷酮的质量为由该金属盐水溶液合成的Ni1-x-yCoxMny(OH)2的质量的1%。
配制300mL氢氧化钠与氨水的混合溶液，该混合溶液中氢氧化钠的浓度为0.02mol/L，氨水的浓度为0.04mol/L。
在30℃及氩气保护的条件下，通过蠕动泵将上述带有聚乙烯吡咯烷酮的金属盐水溶液、氢氧化钠与氨水的混合溶液同时缓慢加入反应容器中反应12小时，得到镍钴锰的共沉淀物。
用去离子水将上述沉淀物洗净从而得到三元正极材料前驱体。
将上述三元正极材料前驱体配制成200mL的三元正极材料前驱体的悬浊液，其中，该悬浊液中三元正极材料前驱体的质量百分比浓度为8%。
搅拌上述三元正极材料前驱体的悬浊液，同时按Li:（Ni+Co+Mn）=1.05:1的摩尔比往该三元正极材料前驱体的悬浊液中加入丙烯酸锂。
在50℃的温度下往上述带丙烯酸锂的三元正极材料前驱体的悬浊液中加入过硫酸铵并搅拌，以使丙烯酸锂进行聚合反应从而得到聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液。其中，过硫酸铵的质量为丙烯酸锂质量的2%，反应时间为8小时。
对上述聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液进行喷雾干燥，得到球状的聚丙烯酸锂包覆的三元正极材料前驱体颗粒。
将上述聚丙烯酸锂包覆的三元正极材料前驱体颗粒在氩气及400℃的条件下烧结3小时，而后在空气及700℃的条件下烧结12小时，从而得到碳包覆三元正极材料。
图1为本实施例1制备的碳包覆三元正极材料的XRD谱图。由图1可以看出，实施例1制得的材料成分为碳包覆三元正极材料，其图谱与碳包覆三元正极材料的标准图谱一致。
图2为本实施例1制备的碳包覆三元正极材料放大10000倍的SEM照片，由图2可以看出，该碳包覆三元正极材料二次颗粒为球形，其粒径为5μm~10μm。
图3为本实施例1制备的碳包覆三元正极材料放大50000倍的SEM照片，图3可以看出，该碳包覆三元正极材料一次颗粒的粒径为200nm~300nm，形状呈规则的片状。
图4为本实施例1制备的碳包覆三元正极材料一次颗粒的透射电镜照片，其中两箭头之间的材料层为碳包覆层，碳包覆层的厚度约为5nm。
图5为实施例1制备的碳包覆三元正极材料作为锂离子电池的正极得到的循环性能曲线图。可以看出，实施例1制得的碳包覆三元正极材料在0.2C、1C、2C、5C、10C的倍率下的放电比容量分别为168mAh/g、148.3mAh/g、135.6mAh/g、120mAh/g、95.2mAh/g，经过倍率循环之后重新在0.2C下循环其比容量依旧保持在160mAh/g左右，说明实施例1制得的碳包覆三元正极材料的循环性能较佳。
图6为实施例1制备的碳包覆三元正极材料作为锂离子电池的正极得到的倍率充放电性能图，可以看出，实施例1制得的碳包覆三元正极材料在常温常压下，用1C的电流对其进行充放电循环时，首次放电容量为145.7mAh/g，经过100次循环之后的放电容量为131.7 mAh/g，容量保持率为90.2%，说明实施例1制得的碳包覆三元正极材料的倍率性能较佳。实施例1制备的碳包覆三元正极材料具有良好的电化学性能。
实施例2
将硫酸镍、硫酸钴、硫酸锰按照Ni:Co:Mn=8:1:1的摩尔比配制300mL浓度为1mol/L的金属盐水溶液。
往上述金属盐水溶液中加入聚乙烯吡咯烷酮并搅拌直至完全溶解。其中，聚乙烯吡咯烷酮的质量为由该金属盐水溶液合成的Ni1-x-yCoxMny(OH)2的质量的3%。
配制300mL氢氧化钠与氨水的混合溶液，该混合溶液中氢氧化钠的浓度为2mol/L，氨水的浓度为4mol/L。
在28℃及氩气保护的条件下，通过蠕动泵将上述带有聚乙烯吡咯烷酮的金属盐水溶液、氢氧化钠与氨水的混合溶液同时缓慢加入反应容器中反应12小时，得到镍钴锰的共沉淀物。
用去乙醇将上述沉淀物洗净从而得到三元正极材料前驱体。
将上述三元正极材料前驱体配制成200mL的三元正极材料前驱体的悬浊液，其中，该悬浊液中三元正极材料前驱体的质量百分比浓度为8%。
一边搅拌上述三元正极材料前驱体的悬浊液一边按Li:（Ni+Co+Mn）=1.05:1的摩尔比往该三元正极材料前驱体的悬浊液中加入丙烯酸锂。
在60℃的温度下往上述带丙烯酸锂的三元正极材料前驱体的悬浊液中加入过硫酸铵并搅拌，以使丙烯酸锂进行聚合反应从而得到聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液。其中，过硫酸铵的质量为丙烯酸锂质量的5%，反应时间为8小时。
对上述聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液进行喷雾干燥，得到球状的聚丙烯酸锂包覆的三元正极材料前驱体颗粒。
将上述聚丙烯酸锂包覆的三元正极材料前驱体颗粒在氩气及500℃的条件下烧结6小时，而后在空气及1000℃的条件下烧结20小时，从而得到碳包覆三元正极材料。
另外，对于本领域的普通技术人员来说，可以根据本发明的技术构思做出其它各种相应的改变与变形，而所有这些改变与变形都应属于本发明权利要求的保护范围。

Claims (9)

  1. 一种碳包覆三元正极材料的制备方法，该三元正极材料的化学式为LiNi1-x-yCoxMnyO2，其中0<x≤0.4，0<y≤0.3，该制备方法包括如下步骤：
    以镍盐、钴盐、锰盐为原料，反应制备镍钴锰的共沉淀物作为三元正极材料前驱体；
    制备上述三元正极材料前驱体的悬浊液，该悬浊液中该三元正极材料前驱体的质量百分比浓度为5%~30%；
    按Li:（Ni+Co+Mn）为1.03~1.05:1的摩尔比往该三元正极材料前驱体的悬浊液中加入丙烯酸锂；
    在50℃~80℃的温度下往该加有丙烯酸锂的三元正极材料前驱体的悬浊液中加入过硫酸铵，以使丙烯酸锂进行聚合反应生成聚丙烯酸锂并包覆该三元正极材料前驱体颗粒，从而得到聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液，该过硫酸铵的质量为该丙烯酸锂质量的2%~10%，反应时间为5~8小时；
    对上述聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液进行干燥，得到球状聚丙烯酸锂包覆的三元正极材料前驱体颗粒；以及
    对上述聚丙烯酸锂包覆的三元正极材料前驱体颗粒进行烧结，得到碳包覆三元正极材料。
  2. 如权利要求1所述的碳包覆三元正极材料的制备方法，其特征在于：步骤“制备三元正极材料前驱体”具体包括：
    将镍盐、钴盐、锰盐按照Ni:Co:Mn为(1-x-y):x:y的摩尔比配制成金属盐水溶液，其中，0<x≤0.4，0<y≤0.3，该金属盐水溶液的浓度为0.01mol/L~1mol/L；
    往金属盐水溶液中加入表面活性剂，其中，该表面活性剂的质量为可由该金属盐水溶液合成的三元正极材料前驱体的质量的1%~10%；
    在25℃~50℃及惰性气体保护的条件下，将所述加有表面活性剂的金属盐水溶液、氢氧化钠溶液及氨水溶液混合反应得到沉淀物，其中，各组分的摩尔比为（Ni2++Co2++Mn2+）:OH-:NH4 +为1:2:2，反应时间为2~12小时；以及
    清洗沉淀物，从而得到三元正极材料前驱体。
  3. 如权利要求2所述的碳包覆三元正极材料的制备方法，其特征在于：该镍盐选自硫酸镍、醋酸镍及硝酸镍中的一种或几种，该钴盐选自硫酸钴、醋酸钴及硝酸钴中的一种或几种，该锰盐选自硫酸锰、醋酸锰及硝酸锰中的一种或几种。
  4. 如权利要求2所述的碳包覆三元正极材料的制备方法，其特征在于：该表面活性剂选自聚乙烯吡咯烷酮、聚乙二醇及十六烷基三甲基氯化铵中的一种或几种。
  5. 如权利要求2所述的碳包覆三元正极材料的制备方法，其特征在于：步骤“在25℃~50℃及惰性气体保护的条件下，将带有表面活性剂的金属盐水溶液、氢氧化钠溶液及氨水溶液混合反应得到沉淀物”还进一步包括：
    对混合后的带有表面活性剂的金属盐水溶液、氢氧化钠溶液及氨水溶液时进行超声震荡。
  6. 如权利要求1所述的碳包覆三元正极材料的制备方法，其特征在于：步骤“对上述聚丙烯酸锂包覆的三元正极材料前驱体的悬浊液进行干燥”中的干燥方法为喷雾干燥。
  7. 如权利要求1所述的碳包覆三元正极材料的制备方法，其特征在于：步骤“对上述聚丙烯酸锂包覆的三元正极材料前驱体颗粒进行烧结，得到碳包覆三元正极材料”具体包括：
    将聚丙烯酸锂包覆的三元正极材料前驱体颗粒在惰性气体及300℃~500℃的条件下预烧3~12小时；以及
    在空气及700℃~1000℃的条件下烧结12~24小时。
  8. 一种如权利要求1-7任意一项所述制备方法制备的碳包覆三元正极材料。
  9. 一种锂离子电池，包括正极，其特征在于：该正极包括如权利要求1-7任意一项所述制备方法制备的碳包覆三元正极材料。
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CN114261996B (zh) * 2021-12-24 2023-09-22 广西师范大学 一种表面完全修饰的单晶高镍三元材料的制备方法及应用
CN115092977A (zh) * 2022-07-07 2022-09-23 楚能新能源股份有限公司 一种三元正极材料的制备方法
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CN115286051B (zh) * 2022-08-09 2023-06-27 荆门市格林美新材料有限公司 一种四元正极前驱体及其制备方法和应用
CN115724420A (zh) * 2022-09-30 2023-03-03 重庆长安新能源汽车科技有限公司 一种双金属掺杂多孔碳材料、制备方法、应用及其包覆正极材料和制备方法
CN115724420B (zh) * 2022-09-30 2024-04-16 深蓝汽车科技有限公司 一种双金属掺杂多孔碳材料、制备方法、应用及其包覆正极材料和制备方法

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