WO2011009231A1 - Method for preparing carbon-coated positive material of lithium ion battery - Google Patents

Method for preparing carbon-coated positive material of lithium ion battery Download PDF

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Publication number
WO2011009231A1
WO2011009231A1 PCT/CN2009/001120 CN2009001120W WO2011009231A1 WO 2011009231 A1 WO2011009231 A1 WO 2011009231A1 CN 2009001120 W CN2009001120 W CN 2009001120W WO 2011009231 A1 WO2011009231 A1 WO 2011009231A1
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compound
hours
lithium
preparation
carbon
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PCT/CN2009/001120
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French (fr)
Chinese (zh)
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刘昊
吕豪杰
陈军
雷良育
邓龙征
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万向电动汽车有限公司
万向集团公司
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Publication of WO2011009231A1 publication Critical patent/WO2011009231A1/en

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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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 field of lithium ion batteries, and in particular relates to a preparation method of a carbon coated lithium ion battery cathode material. Background technique
  • the positive electrode material is also an important component of the lithium ion battery.
  • LiM0 2 has high cost, poor resources and poor overcharge resistance
  • LiNi0 2 is difficult to prepare and has poor thermal stability
  • LiMn 2 0 4 is rich in resources, cheap and non-toxic, but its capacity is low, high temperature stability and cycle stability are better. difference.
  • LiFeP0 4 raw material has a wide source, low price, no environmental pollution, the thermal stability of the material is good, and the safety performance of the prepared battery is outstanding, so that In the field of various mobile power supplies, especially for large power supplies required for electric vehicles, there is great market prospect.
  • This large power source has low volume specific capacity requirements for materials, and has material price, safety and environmental performance. The demand is higher, making LiFeP0 4 the cathode material for a new generation of lithium-ion battery that has the most development and application potential.
  • phase LiFeP0 4 has a significant disadvantage - low conductivity ( Left and right), the rate of electron conduction and lithium ion migration is very slow, which restricts the performance of its electrical properties and cannot be used as a positive electrode material for lithium ion batteries.
  • the first method is the method adopted by the patent family WO1997040541 and WO 2006130766 owned by the University of Texas.
  • the method is characterized in that in addition to the lithium source, the phosphorus source and the divalent iron source, the raw material is added with organic matter as a carbon source, and LiFeP0 is synthesized at a high temperature.
  • the organic matter is simultaneously decomposed, so that C coats the surface of the LiFeP0 4 material, thereby improving the conductivity of the material, and the effect is very obvious, but the raw materials and the organic carbon source are liberated greatly in the synthesis process by this method.
  • the amount of gas there are major losses, low input-output ratio, high product porosity, low tap density, small particle size, irregular product morphology, and difficult batch control stability.
  • Scheme 2 is the US7422823 B2 patent applied by Valence, which is characterized in that in addition to the lithium source, the phosphorus source and the ferric source, the raw material is also added with inorganic conductive carbon, and the ferric iron is reduced at a high temperature to synthesize the LiFeP0 4 material. At the same time, C is coated on the surface of the material to improve the conductivity of the material.
  • the method has simple process, only a small amount of gas is generated in the synthesis process, the weight loss is small, the input-output ratio is high, the tap density is high, the particle size is moderate, the shape is easy to control, and the batch stability is good, but the product synthesized by the method is used as the positive electrode. In the process of actual use of materials, there are disadvantages such as relatively low gram capacity and relatively poor rate performance.
  • Scheme 3 is the WO 2007030816 and US 20070190418 patents applied by A123.
  • the nano-scale product is prepared by doping metal ions and controlling the material morphology to improve the conductivity, but this method is synthesized.
  • the nano-scale LiFeP0 4 material that is produced is costly and has poor processability when manufacturing battery pole pieces. Summary of the invention
  • the object of the present invention is to provide a new method for preparing a carbon-coated lithium ion battery cathode material.
  • the obtained material has excellent discharge performance, high specific capacity, rate discharge and good safety performance.
  • a method for preparing a carbon-coated lithium ion battery cathode material comprising the following steps in sequence:
  • the precursor is pre-fired at 200 ⁇ 500 ° C for 2 to 10 hours, followed by secondary sintering at 500 to 800 ° C for 2 to 24 hours;
  • step 3 After the product obtained in step 2 is cooled to room temperature and then pulverized, a material conforming to the general formula C-Li x M ⁇ M' y (X0 4 ) n can be obtained, wherein 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 0.5, l ⁇ n ⁇ 1.5, M is a transition metal element, M' is at least one selected from the group consisting of Mg, Ti, Cr, V or Al, and X is selected from S, P or Si.
  • the raw materials of the lithium ion positive electrode material are selected from the above Li compound, M compound, M' compound, X compound such as lithium source, phosphorus source and divalent iron source, and inorganic conductive carbon is added as a conductive agent, and the obtained mixture is passed.
  • the morphology of the product can be regulated, and the inorganic conductive carbon is evenly distributed in the precursor; during the subsequent sintering process, the inorganic conductive carbon and Li x M M' y (X0 4 ) n Produces good cross-linking, which improves the conductivity of the material Sex.
  • the method of the present invention overcomes the shortcomings of several solutions described in the background art, and the prepared
  • Materials such as LiFeP0 4 have excellent overall properties.
  • the compound of M in the step 1 is selected from one of iron, manganese, cobalt or nickel salts.
  • the iron salt refers to a divalent iron salt, and preferably an iron oxalate salt or an iron acetate salt.
  • the Li compound in the step 1 is at least one selected from the group consisting of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate or lithium nitrate. More preferably, at least one of lithium carbonate, lithium hydroxide or lithium acetate.
  • the inorganic conductive carbon in the step 1 is selected from the group consisting of natural graphite, artificial graphite micropowder, carbon black particles, acetylene black particles, carbon nanotubes, nano carbon fibers or organic matter after high temperature pyrolysis. At least one of the obtained inorganic carbons.
  • the organic substance is one or more selected from the group consisting of a polymer and an oligomer containing a carbon skeleton, a simple carbohydrate or polymer, and an organic compound of an aromatic hydrocarbon. More than one mixture.
  • the organic substance is selected from the group consisting of polyvinyl alcohol, styrene-butadiene rubber latex, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, poly At least one of vinylidene fluoride, polypropylene eye, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose or starch.
  • the solvent in the step 1 is at least selected from the group consisting of deionized water, ethanol, ethylene glycol, propanol, isopropanol, n-butanol, glycerin or ethylenediamine.
  • the solvent in the step 1 is at least selected from the group consisting of deionized water, ethanol, ethylene glycol, propanol, isopropanol, n-butanol, glycerin or ethylenediamine.
  • the solvent in the step 1 is at least selected from the group consisting of deionized water, ethanol, ethylene glycol, propanol, isopropanol, n-butanol, glycerin or ethylenediamine.
  • it is at least one of deionized water, ethanol or ethylene glycol.
  • the spray granulation in the step 1 employs a centrifugal spray granulation dryer.
  • the gas in the step 2 is at least one of hydrogen, nitrogen or argon. More preferably, it is nitrogen or hydrogen or a mixture thereof in any ratio.
  • the calcination in the step 2 is carried out at 300 to 500 ° C for 4 to 8 hours.
  • the secondary sintering in the step 2 is carried out at 550 to 780 ° C for 5 to 20 hours.
  • the pulverization in the step 3 is carried out by using an ultrafine pulverizer, a jet mill, a mechanical pulverizer or a composite pulverizer. More preferably, an ultrafine pulverizer or a composite pulverizer is used.
  • the present invention has the following advantages -
  • the method of the invention has the advantages of simple operation and low cost; the obtained cL v ⁇ y M' y (xo 4 ) n material has good conductivity, single structure and no impurity phase, and the material has high specific capacity, rate discharge and safety performance. Good features, suitable for power batteries; its preparation method is easy to industrialize.
  • Figure 1 is a crystal phase diagram of the material prepared in Example 1; (2 ⁇ ⁇ , ⁇ 6000 times.)
  • Figure 2 is an XRD diffraction pattern of the material prepared in Example 1.
  • Figure 3 is a graph showing the charge and discharge curves of the materials prepared in Example 1 and Comparative Example, wherein " ⁇ is the 0.2C discharge curve of the material of Example 1, one" - the 0.2C discharge curve of the comparative material, and the material of Example 1 is 0.2.
  • C charging curve one is the 0.2C charging curve of the comparative material.
  • Figure 4 is a 0.2C cycle diagram of the material prepared in Example 1.
  • Example 5 is a rate discharge curve of the material prepared in Example 1, wherein one is a 15C discharge curve, ⁇ is an 8C discharge curve, one is a 5C discharge curve, and one is a 3C discharge curve, "" is a 1C discharge curve, ⁇ ⁇ is the 0.3C discharge curve.
  • Figure 6 is a rate discharge curve of the material prepared in the comparative example, wherein "" is a 15C discharge curve, _ is an 8C discharge curve, - # ⁇ is a 5C discharge curve, ⁇ is a 3C discharge curve, and one is a 1C discharge Curve, " ⁇ is a 0.3C discharge curve.
  • Example 2 Add 10 mol of lithium hydroxide, 10 mol of ferrous acetate, 10 mol of NH 2 P0 4 , 3000 ml of deionized water and 160 g of acetylene black to a ball mill jar, and simultaneously add 8 mm diameter zirconia grinding balls, and ball mill for 6 hours at 300 r/min.
  • the carbon obtained by pyrolyzing lOmol lithium acetate, lOmol ammonium ferrous phosphate, 3500 ml ethanol and 200 g phenolic resin was added to a ball mill jar, and a 10 mm diameter zirconia grinding ball was added, and ball milling was performed at 350 r/min for 6 hours to obtain uniformity.
  • the slurry mixture is spray-dried by a centrifugal spray granulation dryer to obtain a precursor; the precursor is placed in an atmosphere protection tube furnace, nitrogen gas is introduced, and the temperature is maintained at 35 CTC for 8 hours, and then the temperature is raised to 800 °.
  • the carbon obtained by pyrolyzing 5 mol of Li 2 C0 3 , 10 mol of ferrous oxalate, 10 mol of (NH 4 ) 3 P0 4 , 4000 ml of ethanol and 50 g of epoxy resin was added to a ball mill jar while adding a 10 mm diameter zirconia mill ball.
  • the carbon obtained by pyrolyzing 5 mol of Li 2 C0 3 , 9.8 mol of ferrous oxalate, 0.2 mol of MgO 2 , 10 mol of (NH 4 ) 3 P0 4 , 4000 ml of ethanol and 50 g of epoxy resin was added to a ball mill jar while adding 8 mm of oxidation.
  • the zirconium grinding ball was ball milled at 350 r/min for 10 hours to obtain a uniform slurry mixture; then spray-dried at 200 ° C with a centrifugal spray granulation dryer to obtain a precursor; the precursor was placed in an atmosphere protection tube
  • the furnace was purged with nitrogen, and incubated at 400 ° C for 10 h, then heated to 650 ° C and kept at a constant temperature for 12 hours, and naturally cooled to room temperature; the above materials were added to an ultrafine pulverizer, and the obtained pulverized material was dried at 120 ° C.
  • a 300 mesh shaker was passed to obtain a C-LiFe G. 98 Mg Q2 P0 4 product.
  • the lOmol lithium hydroxide, lOmol ferrous acetate, 5mol Fe 2 0 3, 3000ml deionised water and 210g of acetylene black was added to the ball mill jar, while adding 8 mm in diameter zirconia grinding balls, under 350r / mi n milling speed 8 In an hour, a uniform slurry mixture is obtained; and then dried by a vacuum dryer to obtain a precursor; the precursor is placed in an atmosphere protection tube furnace, nitrogen and hydrogen are introduced, and the temperature is maintained at 450 ° C for 8 hours, and then the temperature is raised to The mixture was heated to room temperature at 700 ° C for 12 hours, and naturally cooled to room temperature.
  • the above materials were pulverized by an ultrafine pulverizer, and the obtained pulverized product was dried at 100 ° C for 8 hours and passed through a 300-mesh shake sieve to obtain a C-LiFePO 4 product. Performance Testing
  • Examples 1-9 and Comparative Examples were prepared.
  • - ⁇ ⁇ ⁇ ' ⁇ ( ⁇ 04) ⁇ product, conductive carbon black, polytetrafluoroethylene (PTFE) is uniformly mixed in a certain mass ratio (85: 10: 5), and then an appropriate amount of nitromethylpyrrolidone is added.
  • the Winner 2000 laser particle size tester analyzes the sample.
  • the sample was analyzed by the SSA-3500 specific surface area tester.
  • the sample was analyzed by BT-300 powder tap density meter.
  • the material obtained by the method of the present invention has good conductivity, high capacity, good rate performance, uniform particle size distribution and easy control.

Abstract

A method for preparing a carbon-coated positive material of a lithium ion battery is provided. The formula of the positive material is C-LixM(1-y)M'y(XO4)n, wherein 0<x≤2, 0≤y≤0.5, 1≤n≤1.5, and M is a transition metal; M' is one of Mg, Ti, Cr, V or Al; and X is S, P or Si. The method includes: ① mixing lithium compound, M compound, M' compound and X compound with at least one kind of inorganic conductive carbon according to a certain ratio, adding solvent in the mixture and ball milling the mixture, and then performing spray granulation to obtain precursors; ② in a gas protection atmosphere, pre-sintering the precursors at 200-500℃ for 2-10 hours, and then secondary sintering the precursors at 500-800℃ for 2-24 hours; and ③ after the temperature of the product obtained by step ② is reduced to room temperature, crushing the product to obtain the positive material. The positive material has good electrical conductivity, a high specific capacity and an excellent rate discharge performance.

Description

一种碳包覆锂离子电池正极材料的制备方法 技术领域  Preparation method of carbon-coated lithium ion battery cathode material
本发明属于锂离子电池领域， 具体涉及一种碳包覆锂离子电池正极材料的制备方法。 背景技术  The invention belongs to the field of lithium ion batteries, and in particular relates to a preparation method of a carbon coated lithium ion battery cathode material. Background technique
锤离子电池作为新一代绿色高能电池， 具有电压高， 能量密度大， 循环性能好， 自放电 小， 无记忆效应， 工作温度范围宽等优点而被广泛应用。 正极材料又是锂离子电池的重要组 成部分， 传统的锂离子蓄电池正极材料集中于锂的过渡金属氧化物如 LiM02 (M=Co, Ni, Mn) 和 LiMn204。 但 LiCo02成本高， 资源贫乏， 耐过充性差； LiNi02制备困难，热稳定性差； LiMn204资源丰富、 价格便宜、 无毒，但其容量较低， 高温稳定性和循环稳定性较差。 As a new generation of green high-energy battery, hammer ion battery has been widely used due to its high voltage, high energy density, good cycle performance, small self-discharge, no memory effect and wide operating temperature range. The positive electrode material is also an important component of the lithium ion battery. The conventional lithium ion battery positive electrode material concentrates on lithium transition metal oxides such as LiM0 2 (M=Co, Ni, Mn) and LiMn 2 0 4 . However, LiCo0 2 has high cost, poor resources and poor overcharge resistance; LiNi0 2 is difficult to prepare and has poor thermal stability; LiMn 2 0 4 is rich in resources, cheap and non-toxic, but its capacity is low, high temperature stability and cycle stability are better. difference.
具有橄榄石结构的通式 LiMP04的***化合物是己知的，其中 M是属于第一行过渡金属， 比如 Mn、 Fe、 Co或 Ni的金属离子； 当基本上保持同样的橄榄石结构时， 一部分磷可以被诸 如 Si、 S等元素取代。 An intercalation compound of the general formula LiMP0 4 having an olivine structure, wherein M is a metal ion belonging to the first row of transition metals, such as Mn, Fe, Co or Ni; when substantially maintaining the same olivine structure, A part of phosphorus may be substituted by an element such as Si, S or the like.
在上述有可能作为正极材料用于锂离子二次电池的选择项中， 由于 LiFeP04原料来源广 泛， 价格低廉， 无环境污染， 材料的热稳定性好， 所制备电池的安全性能突出， 使得其在各 种可移动电源领域， 特别是电动车所需的大型动力电源领域有着极大的市场前景， 这种大型 动力电源对材料的体积比容量要求低， 而对材料价格、 安全性及环保性能要求较高， 从而使 LiFeP04成为最具开发和应用潜力的新一代锂离子电池正极材料。 In the above selection which may be used as a positive electrode material for a lithium ion secondary battery, since the LiFeP0 4 raw material has a wide source, low price, no environmental pollution, the thermal stability of the material is good, and the safety performance of the prepared battery is outstanding, so that In the field of various mobile power supplies, especially for large power supplies required for electric vehicles, there is great market prospect. This large power source has low volume specific capacity requirements for materials, and has material price, safety and environmental performance. The demand is higher, making LiFeP0 4 the cathode material for a new generation of lithium-ion battery that has the most development and application potential.
橄榄石型结构的 LiFeP04相对于钴酸锂、 锰酸锂、 镍酸锂的主要优点在于该材料热稳定 性好， 与电解质之间有高度相容性而具有更高的安全性能， 然而纯相的 LiFeP04存在着一个 明显的缺点一电导率低（
Figure imgf000003_0001
左右）， 电子导电和锂离子迁移速率非常慢， 制约了其电性 能的发挥， 无法在直接作为正极材料用于锂离子电池中。 The main advantage of the olivine-type LiFeP0 4 relative to lithium cobaltate, lithium manganate and lithium nickelate is that the material has good thermal stability and high compatibility with the electrolyte and has higher safety performance. Phase LiFeP0 4 has a significant disadvantage - low conductivity (
Figure imgf000003_0001
Left and right), the rate of electron conduction and lithium ion migration is very slow, which restricts the performance of its electrical properties and cannot be used as a positive electrode material for lithium ion batteries.
为了解决这个问题， 目前业界主要通过以下几种途径来提高其导电性：  In order to solve this problem, the current industry mainly improves its conductivity through the following ways:
方案一为德州大学所拥有的 WO1997040541 , WO 2006130766专利族所采用的方法， 其 特征是原材料除了选用锂源、 磷源和二价铁源之外， 还添加了有机物作为碳源， 在高温合成 LiFeP04的过程中， 有机物同步分解， 使 C包覆在 LiFeP04材料表面， 以此提高材料的导电 性， 效果十分明显， 但是采用此方法的合成过程中由于原材料和有机碳源均剧烈分解放出大 量的气体， 存在着失重大， 投入产出比低， 产物孔隙率高， 振实密度低， 粒度小， 产品的形 貌不规则， 批次稳定性难以控制等缺点。 The first method is the method adopted by the patent family WO1997040541 and WO 2006130766 owned by the University of Texas. The method is characterized in that in addition to the lithium source, the phosphorus source and the divalent iron source, the raw material is added with organic matter as a carbon source, and LiFeP0 is synthesized at a high temperature. In the process of 4 , the organic matter is simultaneously decomposed, so that C coats the surface of the LiFeP0 4 material, thereby improving the conductivity of the material, and the effect is very obvious, but the raw materials and the organic carbon source are liberated greatly in the synthesis process by this method. The amount of gas, there are major losses, low input-output ratio, high product porosity, low tap density, small particle size, irregular product morphology, and difficult batch control stability.
方案二为 Valence公司申请的 US7422823 B2专利， 其特征是原材料除了选用锂源、磷源 和三价铁源之外， 还添加了无机导电碳， 用高温下 C还原三价铁， 合成 LiFeP04材料， 同时 将 C包覆在材料表面， 以此提高材料的导电性。 该方法工艺简单， 合成过程中只产生少量气 体， 失重小， 投入产出比高， 振实密度高， 粒度适中， 形貌易控制， 批次稳定性好， 但这种 方法合成的产品作为正极材料实际使用的过程中存在克容量相对较低， 倍率性能相对较差等 缺点。 Scheme 2 is the US7422823 B2 patent applied by Valence, which is characterized in that in addition to the lithium source, the phosphorus source and the ferric source, the raw material is also added with inorganic conductive carbon, and the ferric iron is reduced at a high temperature to synthesize the LiFeP0 4 material. At the same time, C is coated on the surface of the material to improve the conductivity of the material. The method has simple process, only a small amount of gas is generated in the synthesis process, the weight loss is small, the input-output ratio is high, the tap density is high, the particle size is moderate, the shape is easy to control, and the batch stability is good, but the product synthesized by the method is used as the positive electrode. In the process of actual use of materials, there are disadvantages such as relatively low gram capacity and relatively poor rate performance.
方案三为 A123公司申请的 WO 2007030816， US 20070190418专利， 没有采用 C包覆的 方法， 而是通过掺杂金属离子， 同时控制材料形貌制得纳米级产品来提高导电性， 但这种方 法合成出来的纳米级 LiFeP04材料成本高昂、 制作电池极片时加工性差。 发明内容 Scheme 3 is the WO 2007030816 and US 20070190418 patents applied by A123. Instead of adopting the C coating method, the nano-scale product is prepared by doping metal ions and controlling the material morphology to improve the conductivity, but this method is synthesized. The nano-scale LiFeP0 4 material that is produced is costly and has poor processability when manufacturing battery pole pieces. Summary of the invention
针对上述现有技术存在的诸如材料导电性差、 比容量低、 倍率放电及安全性能差等方面 的缺点， 本发明的目的是提供一种新的涂敷碳的锂离子电池正极材料的制备方法， 使获得的 材料具备优良的放电性能、 比容量高、 倍率放电及安全性能好的特点。  In view of the above-mentioned shortcomings such as poor conductivity, low specific capacity, rate discharge, and poor safety performance of the prior art, the object of the present invention is to provide a new method for preparing a carbon-coated lithium ion battery cathode material. The obtained material has excellent discharge performance, high specific capacity, rate discharge and good safety performance.
为实现本发明的目的， 发明人提供下述技术方案：  In order to achieve the object of the present invention, the inventors provide the following technical solutions:
一种碳包覆锂离子电池正极材料的制备方法， 依次包括下述步骤：  A method for preparing a carbon-coated lithium ion battery cathode material, comprising the following steps in sequence:
①将 Li化合物、 M化合物、 M'化合物、 X化合物和至少一种无机导电碳混合， 所得混合 物加入溶剂后做球磨处理， 球磨产物经喷雾造粒得到前驱体， 其中， 所述混合物中 Li: M: Μ': X的摩尔比 =0.95〜1.05： 0.45〜1.05： 0〜0.55： 0.95〜1.05，无机导电碳含量为 l〜20wt%; 1 a Li compound, an M compound, an M' compound, a X compound, and at least one inorganic conductive carbon are mixed, and the resulting mixture is added to a solvent to be subjected to a ball milling treatment, and the ball milled product is subjected to spray granulation to obtain a precursor, wherein the mixture is Li: M: Μ': X molar ratio = 0.95~1.05: 0.45~1.05: 0~0.55: 0.95~1.05, inorganic conductive carbon content is l~20wt%;
②气体保护氛围下，将前驱体在 200〜500°C预烧 2〜10小时，接着在 500〜800°C下二次 烧结处理 2〜24小时； 2 in a gas atmosphere, the precursor is pre-fired at 200~500 ° C for 2 to 10 hours, followed by secondary sintering at 500 to 800 ° C for 2 to 24 hours;
③待步骤②所得产物冷却至室温后做粉碎即可得到符合通式 C-LixM^M'y(X04)n的材料， 其中， 0<x≤2， 0≤y≤0.5、 l≤n≤1.5， M是过渡金属元素， M'选自 Mg、 Ti、 Cr、 V或 Al 中至少一种， X选自 S、 P或 Si。 3 After the product obtained in step 2 is cooled to room temperature and then pulverized, a material conforming to the general formula C-Li x M^M' y (X0 4 ) n can be obtained, wherein 0<x≤2, 0≤y≤0.5, l ≤ n ≤ 1.5, M is a transition metal element, M' is at least one selected from the group consisting of Mg, Ti, Cr, V or Al, and X is selected from S, P or Si.
发明人研究发现锂离子正极材料的原材料选用上述的 Li化合物、 M化合物、 M'化合物、 X化合物， 如锂源、 磷源和二价铁源， 并添加无机导电碳作为导电剂， 所得混合物通过均勾 球磨后再经造粒强制成型，可以调控产品的形貌， 同时使无机导电碳均匀分布于前躯体之中； 在后续烧结过程中无机导电碳与 LixM M'y(X04)n产生很好的交联， 从而提高了材料的导电 性。 本发明的方法克服了背景技术中所述的几种方案的缺点， 制备出的
Figure imgf000005_0001
The inventors have found that the raw materials of the lithium ion positive electrode material are selected from the above Li compound, M compound, M' compound, X compound such as lithium source, phosphorus source and divalent iron source, and inorganic conductive carbon is added as a conductive agent, and the obtained mixture is passed. After being ball-milled and then forced by granulation, the morphology of the product can be regulated, and the inorganic conductive carbon is evenly distributed in the precursor; during the subsequent sintering process, the inorganic conductive carbon and Li x M M' y (X0 4 ) n Produces good cross-linking, which improves the conductivity of the material Sex. The method of the present invention overcomes the shortcomings of several solutions described in the background art, and the prepared
Figure imgf000005_0001
材料， 如 LiFeP04材料具有优秀的综合性能。 Materials such as LiFeP0 4 have excellent overall properties.
作为优选方案， 根据本发明所述的制备方法， 其步骤①中的 M化合物选自铁、 锰、 钴或 镍盐中一种。  Preferably, according to the preparation method of the present invention, the compound of M in the step 1 is selected from one of iron, manganese, cobalt or nickel salts.
作为优选方案， 根据本发明所述的制备方法， 其步骤①中所述的 M化合物选用铁盐时， 铁盐指二价铁盐， 优选选用草酸铁盐或醋酸铁盐。  Preferably, according to the preparation method of the present invention, when the M compound described in the step 1 is an iron salt, the iron salt refers to a divalent iron salt, and preferably an iron oxalate salt or an iron acetate salt.
作为优选方案， 根据本发明所述的制备方法， 其步骤①中的 Li化合物选自碳酸锂、氢氧 化锂、 磷酸二氢锂、 醋酸锂或硝酸锂中至少一种。 更优选碳酸锂、 氢氧化锂或醋酸锂中至少 一种。  Preferably, according to the preparation method of the present invention, the Li compound in the step 1 is at least one selected from the group consisting of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate or lithium nitrate. More preferably, at least one of lithium carbonate, lithium hydroxide or lithium acetate.
作为优选方案， 根据本发明所述的制备方法， 其步骤①中的无机导电碳选自天然石墨、 人造石墨微粉、 碳黑颗粒、 乙炔黑颗粒、 碳纳米管、 纳米碳纤维或有机物高温热解后所得到 的无机碳中的至少一种。  Preferably, according to the preparation method of the present invention, the inorganic conductive carbon in the step 1 is selected from the group consisting of natural graphite, artificial graphite micropowder, carbon black particles, acetylene black particles, carbon nanotubes, nano carbon fibers or organic matter after high temperature pyrolysis. At least one of the obtained inorganic carbons.
作为优选方案， 根据本发明所述的制备方法， 上述的有机物选自含有碳骨架的聚合物和 低聚物、 简单的碳水化合物或聚合物以及芳香族烃类的有机化合物中的一种或一种以上的混 合物。  Preferably, according to the preparation method of the present invention, the organic substance is one or more selected from the group consisting of a polymer and an oligomer containing a carbon skeleton, a simple carbohydrate or polymer, and an organic compound of an aromatic hydrocarbon. More than one mixture.
作为优选方案， 根据本发明所述的制备方法， 上述的有机物选自聚乙烯醇、丁苯橡胶乳、 羧甲基纤维素、 聚苯乙烯、 聚甲基丙烯酸甲酯、 聚四氟乙烯、 聚偏氟乙烯、 聚丙烯睛、 酚醛 树脂、 环氧树脂、 葡萄糖、 蔗糖、 果糖、 纤维素或淀粉中至少一种。  Preferably, according to the preparation method of the present invention, the organic substance is selected from the group consisting of polyvinyl alcohol, styrene-butadiene rubber latex, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, poly At least one of vinylidene fluoride, polypropylene eye, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose or starch.
作为优选方案， 根据本发明所述的制备方法， 其步骤①中的溶剂选自去离子水、 乙醇、 乙二醇、 丙醇、 异丙醇、 正丁醇、 甘油或乙二胺中的至少一种。 更优选为去离子水、 乙醇或 乙二醇中至少一种。  Preferably, according to the preparation method of the present invention, the solvent in the step 1 is at least selected from the group consisting of deionized water, ethanol, ethylene glycol, propanol, isopropanol, n-butanol, glycerin or ethylenediamine. One. More preferably, it is at least one of deionized water, ethanol or ethylene glycol.
作为优选方案， 根据本发明所述的制备方法， 其步骤①中的喷雾造粒采用离心式喷雾造 粒干燥机。  Preferably, according to the preparation method of the present invention, the spray granulation in the step 1 employs a centrifugal spray granulation dryer.
作为优选方案， 根据本发明所述的制备方法， 其步骤②中的气体为氢气、 氮气或氩气中 的至少一种。 更优选为氮气或氢气或其任意比例的混合物。  Preferably, according to the preparation method of the present invention, the gas in the step 2 is at least one of hydrogen, nitrogen or argon. More preferably, it is nitrogen or hydrogen or a mixture thereof in any ratio.
作为优选方案， 根据本发明所述的制备方法， 其步骤②中的预烧为在 300〜500°C下处理 4〜8小时。  Preferably, according to the preparation method of the present invention, the calcination in the step 2 is carried out at 300 to 500 ° C for 4 to 8 hours.
作为优选方案， 根据本发明所述的制备方法， 其步骤②中的二次烧结为在 550〜780°C下 处理 5-20小时。  Preferably, according to the preparation method of the present invention, the secondary sintering in the step 2 is carried out at 550 to 780 ° C for 5 to 20 hours.
作为优选方案， 根据本发明所述的制备方法， 其步骤③中的粉碎采用超微粉碎机、 气流 粉碎机、 机械式粉碎机或复合粉碎机。 更优选采用超微粉碎机或复合粉碎机。  Preferably, according to the preparation method of the present invention, the pulverization in the step 3 is carried out by using an ultrafine pulverizer, a jet mill, a mechanical pulverizer or a composite pulverizer. More preferably, an ultrafine pulverizer or a composite pulverizer is used.
与现有技术相比， 本发明具有以下优点- 本发明方法操作简单，成本较低；制得的 c-L v^yM'y(xo4)n材料其导电性好，结构单一， 不含杂相， 材料具有比容量高、 倍率放电及安全性能好的特点， 适合于动力电池； 其制备方 法易于工业化生产。 附图说明 Compared with the prior art, the present invention has the following advantages - The method of the invention has the advantages of simple operation and low cost; the obtained cL v^ y M' y (xo 4 ) n material has good conductivity, single structure and no impurity phase, and the material has high specific capacity, rate discharge and safety performance. Good features, suitable for power batteries; its preparation method is easy to industrialize. DRAWINGS
图 1是实施例 1制备的材料的晶相图； （2 μ ιη， Χ 6000倍。）  Figure 1 is a crystal phase diagram of the material prepared in Example 1; (2 μ ιη, Χ 6000 times.)
图 2是实施例 1制备的材料的 XRD衍射图谱。  Figure 2 is an XRD diffraction pattern of the material prepared in Example 1.
图 3是实施例 1和比较例制备的材料的充放电曲线图， 其中， "^是实例 1材料 0.2C 放电曲线， 一》—比较例材料 0.2C放电曲线， 一》~是实例 1材料 0.2C充电曲线，一 ·一是 比较例材料 0.2C充电曲线。  Figure 3 is a graph showing the charge and discharge curves of the materials prepared in Example 1 and Comparative Example, wherein "^ is the 0.2C discharge curve of the material of Example 1, one" - the 0.2C discharge curve of the comparative material, and the material of Example 1 is 0.2. C charging curve, one is the 0.2C charging curve of the comparative material.
图 4是实施例 1制备的材料的 0.2C循环曲线图。  Figure 4 is a 0.2C cycle diagram of the material prepared in Example 1.
图 5是实施例 1制备的材料的倍率放电曲线，其中， 一 是 15C放电曲线， →~是 8C放电曲线， 一是 5C放电曲线， 一♦一是 3C放电曲线， ""是 1C放电曲线， ^ ^ 是 0.3C放电曲线。  5 is a rate discharge curve of the material prepared in Example 1, wherein one is a 15C discharge curve, →~ is an 8C discharge curve, one is a 5C discharge curve, and one is a 3C discharge curve, "" is a 1C discharge curve, ^ ^ is the 0.3C discharge curve.
图 6是比较例制备的材料的倍率放电曲线，其中， 一 ""是 15C放电曲线， _ 是 8C 放电曲线， — #一是 5C放电曲线， ^ ^是 3C放电曲线， 一♦一是 1C放电曲线， "^是 0.3C放电曲线。 具体实施方式  Figure 6 is a rate discharge curve of the material prepared in the comparative example, wherein "" is a 15C discharge curve, _ is an 8C discharge curve, - #一 is a 5C discharge curve, ^^ is a 3C discharge curve, and one is a 1C discharge Curve, "^ is a 0.3C discharge curve.
下面结合实施例， 更具体地说明本发明的内容。 应当理解， 本发明的实施并不局限于下 面的实施例， 对本发明所做的任何形式上的变通和 /或改变都将落入本发明保护范围。  The contents of the present invention will be more specifically described below with reference to the embodiments. It is to be understood that the invention is not limited to the embodiments described below, and any form of modifications and/or changes made to the invention will fall within the scope of the invention.
在本发明中， 若非特指， 所有的份、 百分比均为重量单位， 所有的设备和原料等均可从 市场购得或是本行业常用的。  In the present invention, unless otherwise specified, all parts and percentages are by weight, and all equipment and materials are commercially available or commonly used in the industry.
实施例 1  Example 1
将 5mol Li2C03、 lOmol FeC204 · 2H20、 lOmol (N ) 2HP04、 3000ml乙醇和 lOOg碳纳 米管加入到球磨罐中， 同时加入直径 10 mm氧化锆碾磨球， 350r/min转速下球磨 8小时， 获 得均匀的浆状混合物料； 然后用离心式喷雾造粒干燥机 200°C喷雾干燥， 得到前驱体； 将上 述前驱体放入气氛保护管式炉， 通入氮气， 于 400 °C下保温 3h， 然后升温到 700°C并恒温 6 小时， 自然冷却至室温； 将上述材料加入到超微粉碎机粉碎， 所得粉碎物于 10(TC干燥 10小 时后过 300目震动筛， 得到 C-LiFeP04产品。 Adding 5 mol of Li 2 C0 3 , 10 mol of FeC 2 0 4 · 2H 2 0, 10 mol of (N ) 2 HP0 4 , 3000 ml of ethanol and 100 g of carbon nanotubes to a ball mill jar while adding a 10 mm diameter zirconia grinding ball, 350r Ball milling for 8 hours at /min speed to obtain a uniform slurry mixture; then spray drying with a centrifugal spray granulation dryer at 200 ° C to obtain a precursor; the precursor was placed in an atmosphere protection tube furnace, and nitrogen gas was introduced. , kept at 400 ° C for 3 h, then warmed to 700 ° C and kept at a constant temperature for 6 hours, and naturally cooled to room temperature; the above materials were added to an ultrafine pulverizer, and the obtained pulverized material was passed through 10 mesh after 10 hours of TC drying for 10 hours. Vibrating the sieve to obtain a C-LiFeP0 4 product.
实施例 2 将 lOmol氢氧化锂， lOmol醋酸亚铁、 lOmol N H2P04, 3000ml去离子水和 160g乙炔 黑加入到球磨罐中， 同时加入直径 8 mm氧化锆碾磨球， 300r/min转速下球磨 6小时， 获得 均匀的浆状混合物料； 然后用离心式喷雾造粒干燥机 180Ό喷雾干燥， 得到前驱体； 将上述 前驱体放入气氛保护管式炉， 通入氮气和氢气 （体积比 97: 3 )， 于 380 下保温 8h， 然后升 温到 600°C并恒温 12小时， 自然冷却至室温； 将上述材料加入到超微粉碎机粉碎， 所得粉碎 物于 110°C干燥 6小时后过 300目震动筛， 得到 C-LiFeP04产品。 Example 2 Add 10 mol of lithium hydroxide, 10 mol of ferrous acetate, 10 mol of NH 2 P0 4 , 3000 ml of deionized water and 160 g of acetylene black to a ball mill jar, and simultaneously add 8 mm diameter zirconia grinding balls, and ball mill for 6 hours at 300 r/min. , obtaining a uniform slurry mixture; then spray drying with a centrifugal spray granulation dryer 180 , to obtain a precursor; placing the precursor into an atmosphere protection tube furnace, introducing nitrogen gas and hydrogen gas (volume ratio 97:3) , kept at 380 for 8h, then heated to 600 ° C and kept at constant temperature for 12 hours, naturally cooled to room temperature; the above materials were added to the ultrafine pulverizer, and the obtained pulverized material was dried at 110 ° C for 6 hours and then passed through a 300 mesh vibrating screen. , get C-LiFeP0 4 products.
实施例 3  Example 3
将 lOmol醋酸锂、 lOmol磷酸亚铁铵、 3500ml乙醇和 200g酚醛树脂热解得到的碳加入 到球磨罐中， 同时加入直径 10 mm氧化锆碾磨球， 350r/min转速下球磨 6小时， 获得均匀的 浆状混合物料； 然后用离心式喷雾造粒干燥机 250Ό喷雾干燥， 得到前驱体； 将上述前驱体 放入气氛保护管式炉， 通入氮气， 于 35CTC下保温 8h， 然后升温到 800°C并恒温 8小时， 自 然冷却至室温；将上述材料加入到超微粉碎机粉碎，所得粉碎物于 100°C干燥 15小时后过 300 目震动筛， 得到 C-LiFeP04产品。 The carbon obtained by pyrolyzing lOmol lithium acetate, lOmol ammonium ferrous phosphate, 3500 ml ethanol and 200 g phenolic resin was added to a ball mill jar, and a 10 mm diameter zirconia grinding ball was added, and ball milling was performed at 350 r/min for 6 hours to obtain uniformity. Then, the slurry mixture is spray-dried by a centrifugal spray granulation dryer to obtain a precursor; the precursor is placed in an atmosphere protection tube furnace, nitrogen gas is introduced, and the temperature is maintained at 35 CTC for 8 hours, and then the temperature is raised to 800 °. C and kept at a constant temperature for 8 hours, and naturally cooled to room temperature; the above materials were added to an ultrafine pulverizer, and the obtained pulverized product was dried at 100 ° C for 15 hours and passed through a 300 mesh shaker to obtain a C-LiFeP0 4 product.
实施例 4  Example 4
将 3mol碳酸锂、 4mol醋酸锂、 lOmol醋酸亚铁、 lOmol (N ) 3P04、 4000ml乙醇和 50g纳米碳纤维加入到球磨罐中， 同时加入直径 8 mm氧化锆碾磨球， 380r/min转速下球磨 8 小时， 获得均匀的浆状混合物料； 然后用离心式喷雾造粒干燥机 200°C喷雾干燥， 得到前驱 体； 将上述前驱体放入气氛保护管式炉， 通入氮气， 于 450°C下保温 6h, 然后升温到 600°C 并恒温 10小时， 自然冷却至室温； 将上述材料加入到超微粉碎机粉碎， 所得粉碎物于 120°C 干燥 4小时后过 300目震动筛， 得到 C-LiFeP04产品。 Adding 3 mol of lithium carbonate, 4 mol of lithium acetate, 10 mol of ferrous acetate, 10 mol of (N) 3 P0 4 , 4000 ml of ethanol and 50 g of nano carbon fiber to a ball mill jar while adding a zirconia grinding ball of 8 mm in diameter, at a speed of 380 r/min After ball milling for 8 hours, a uniform slurry mixture was obtained; then spray-dried at 200 ° C with a centrifugal spray granulation dryer to obtain a precursor; the precursor was placed in an atmosphere-protected tube furnace, and nitrogen gas was introduced at 450 ° The mixture was kept at C for 6 h, then heated to 600 ° C and kept at a constant temperature for 10 hours, and naturally cooled to room temperature. The above materials were added to an ultrafine pulverizer, and the obtained pulverized material was dried at 120 ° C for 4 hours and passed through a 300-mesh shake sieve to obtain C-LiFeP0 4 product.
实施例 5  Example 5
将 5mol Li2C03、 lOmol磷酸亚铁铵、 3000ml乙二醇和 160g碳纳米管加入到球磨罐中， 同时加入直径 10 mm氧化锆碾磨球， 300r/min转速下球磨 10小时， 获得均匀的浆状混合物 料； 然后用离心式喷雾造粒干燥机 20(TC喷雾干燥， 得到前驱体； 将上述前驱体放入气氛保 护管式炉， 通入氮气， 于 400°C下保温 8h， 然后升温到 700°C并恒温 12小时， 自然冷却至室 温；将上述材料加入到超微粉碎机粉碎，所得粉碎物于 100°C干燥 10小时后过 300目震动筛， 得到 C-LiFeP04产品。 5 mol of Li 2 C0 3 , 10 mol of ammonium ferrous phosphate, 3000 ml of ethylene glycol and 160 g of carbon nanotubes were added to a ball mill jar, and a 10 mm diameter zirconia grinding ball was added, and ball milling was carried out for 10 hours at 300 r/min to obtain a uniform The slurry mixture is then sprayed by a centrifugal spray granulation dryer 20 (TC spray drying to obtain a precursor; the precursor is placed in an atmosphere protection tube furnace, nitrogen gas is introduced, and the temperature is maintained at 400 ° C for 8 hours, and then the temperature is raised. The mixture was heated to 700 ° C for 12 hours, and naturally cooled to room temperature. The above materials were added to an ultrafine pulverizer, and the obtained pulverized product was dried at 100 ° C for 10 hours and passed through a 300 mesh shaker to obtain a C-LiFePO 4 product.
实施例 6  Example 6
将 5mol Li2C03、 lOmol草酸亚铁、 lOmol (NH4) 3P04、 4000ml乙醇和 50g环氧树脂热 解得到的碳加入到球磨罐中， 同时加入直径 10 mm氧化锆碾磨球， 300r/min转速下球磨 8小 时， 获得均匀的浆状混合物料； 然后用离心式喷雾造粒干燥机 18(TC喷雾干燥， 得到前驱体; 将上述前驱体放入气氛保护管式炉， 通入氮气， 于 450°C下保温 6h， 然后升温到 600°C并恒 温 12小时， 自然冷却至室温； 将上述材料加入到超微粉碎机粉碎， 所得粉碎物于 100Ό干燥 10小时后过 300目震动筛， 得到 C-LiFeP04产品。 The carbon obtained by pyrolyzing 5 mol of Li 2 C0 3 , 10 mol of ferrous oxalate, 10 mol of (NH 4 ) 3 P0 4 , 4000 ml of ethanol and 50 g of epoxy resin was added to a ball mill jar while adding a 10 mm diameter zirconia mill ball. Ball milling for 8 hours at 300 r/min, obtaining a uniform slurry mixture; then using a centrifugal spray granulation dryer 18 (TC spray drying to obtain a precursor; placing the precursor into an atmosphere protection tube furnace, access Nitrogen, incubated at 450 ° C for 6 h, then warmed to 600 ° C and constant After cooling for 12 hours, it was naturally cooled to room temperature; the above materials were added to an ultrafine pulverizer, and the obtained pulverized product was dried at 100 Torr for 10 hours and passed through a 300-mesh shake sieve to obtain a C-LiFePO 4 product.
实施例 7  Example 7
将 5mol Li2C03、 9.8mol草酸亚铁、 0.2 mol MgO2、 lOmol (NH4) 3P04, 4000ml乙醇和 50g环氧树脂热解得到的碳加入到球磨罐中， 同时加入直径 8 mm氧化锆碾磨球， 350r/min转 速下球磨 10小时，获得均匀的浆状混合物料；然后用离心式喷雾造粒干燥机 200°C喷雾干燥， 得到前驱体； 将上述前驱体放入气氛保护管式炉， 通入氮气， 于 400°C下保温 10h， 然后升温 到 650°C并恒温 12小时， 自然冷却至室温； 将上述材料加入到超微粉碎机粉碎， 所得粉碎物 于 120°C干燥 6小时后过 300目震动筛， 得到 C-LiFeG.98Mg Q2P04产品。 The carbon obtained by pyrolyzing 5 mol of Li 2 C0 3 , 9.8 mol of ferrous oxalate, 0.2 mol of MgO 2 , 10 mol of (NH 4 ) 3 P0 4 , 4000 ml of ethanol and 50 g of epoxy resin was added to a ball mill jar while adding 8 mm of oxidation. The zirconium grinding ball was ball milled at 350 r/min for 10 hours to obtain a uniform slurry mixture; then spray-dried at 200 ° C with a centrifugal spray granulation dryer to obtain a precursor; the precursor was placed in an atmosphere protection tube The furnace was purged with nitrogen, and incubated at 400 ° C for 10 h, then heated to 650 ° C and kept at a constant temperature for 12 hours, and naturally cooled to room temperature; the above materials were added to an ultrafine pulverizer, and the obtained pulverized material was dried at 120 ° C. After 6 hours, a 300 mesh shaker was passed to obtain a C-LiFe G. 98 Mg Q2 P0 4 product.
实施例 8  Example 8
将 4mol碳酸锂、2mol醋酸锂、9.85mol 四水醋酸锰、 0.15mol氧化钛、 10moKNH4)2HPO4、 4000ml乙醇和 70g纳米碳纤维加入到球磨罐中，同时加入直径 8 mm氧化锆碾磨球， 500r/min 转速下球磨 10小时， 获得均匀的浆状混合物料； 然后用离心式喷雾造粒干燥机 280°C喷雾干 燥， 得到前驱体； 将上述前驱体放入气氛保护管式炉， 通入氮气， 于 475°C下保温 12h， 然后 升温到 800°C并恒温 10小时， 自然冷却至室温； 将上述材料加入到超微粉碎机粉碎， 所得粉 碎物于 120°C干燥 8小时后过 300目震动筛， 得到 C-LiMno.985Ti謹 5P04产品。 4 mol of lithium carbonate, 2 mol of lithium acetate, 9.85 mol of manganese acetate tetrahydrate, 0.15 mol of titanium oxide, 10 mol of KNH 4 ) 2 HPO 4 , 4000 ml of ethanol and 70 g of nano carbon fiber were added to a ball mill jar while adding a zirconia grinding ball having a diameter of 8 mm. Ball milling for 10 hours at 500 r/min to obtain a uniform slurry mixture; then spray drying at 280 ° C with a centrifugal spray granulation dryer to obtain a precursor; placing the precursor into an atmosphere-protecting tube furnace, Nitrogen gas was incubated at 475 ° C for 12 h, then heated to 800 ° C and kept at a constant temperature for 10 hours, and naturally cooled to room temperature; the above materials were added to an ultrafine pulverizer, and the obtained pulverized material was dried at 120 ° C for 8 hours and then passed through 300 The vibrating screen is obtained by C-LiMno. 985 Ti 5 P0 4 product.
实施例 9  Example 9
将 lOmol氢氧化锂、 lOmol醋酸亚铁、 lOmol二氧化硅， 3000ml去离子水和 160g乙炔 黑加入到球磨罐中， 同时加入直径 10mm氧化锆碾磨球， 350r/min转速下球磨 6小时， 获得 均匀的浆状混合物料； 然后用离心式喷雾造粒干燥机 200°C喷雾干燥， 得到前驱体； 将上述 前驱体放入气氛保护管式炉， 通入氮气和氢气 （体积比 95: 5)， 于 480°C下保温 12h， 然后 升温到 750°C并恒温 18小时， 自然冷却至室温； 将上述材料加入到超微粉碎机粉碎， 所得粉 碎物于 120°C干燥 6小时后过 300目震动筛， 得到 C-LiFeSi04产品。 比较例 10 mol of lithium hydroxide, 10 mol of ferrous acetate, 10 mol of silica, 3000 ml of deionized water and 160 g of acetylene black were added to a ball mill jar, and a 10 mm diameter zirconia mill ball was added, and ball milled at 350 r/min for 6 hours. a uniform slurry mixture; then spray-dried at 200 ° C with a centrifugal spray granulation dryer to obtain a precursor; the precursor is placed in an atmosphere-protected tube furnace, and nitrogen and hydrogen are introduced (volume ratio 95: 5). , incubated at 480 ° C for 12 h, then warmed to 750 ° C and constant temperature for 18 hours, naturally cooled to room temperature; the above materials were added to the ultrafine pulverizer, the obtained pulverized material was dried at 120 ° C for 6 hours and then passed through 300 mesh Vibrating the sieve to obtain a C-LiFeSi0 4 product. Comparative example
将 lOmol氢氧化锂、 lOmol醋酸亚铁、 5mol Fe203、 3000ml去离子水和 210g乙炔黑加 入到球磨罐中， 同时加入直径 8 mm氧化锆碾磨球， 350r/min转速下球磨 8小时， 获得均匀 的浆状混合物料； 然后用真空干燥机干燥， 得到前驱体； 将上述前驱体放入气氛保护管式炉， 通入氮气和氢气， 于 450'C下保温 8h， 然后升温到 700°C并恒温 12小时， 自然冷却至室温； 将上述材料加入到超微粉碎机粉碎， 所得粉碎物于 100°C干燥 8小时后过 300目震动筛， 得 到 C-LiFeP04产品。 性能测试 The lOmol lithium hydroxide, lOmol ferrous acetate, 5mol Fe 2 0 3, 3000ml deionised water and 210g of acetylene black was added to the ball mill jar, while adding 8 mm in diameter zirconia grinding balls, under 350r / mi n milling speed 8 In an hour, a uniform slurry mixture is obtained; and then dried by a vacuum dryer to obtain a precursor; the precursor is placed in an atmosphere protection tube furnace, nitrogen and hydrogen are introduced, and the temperature is maintained at 450 ° C for 8 hours, and then the temperature is raised to The mixture was heated to room temperature at 700 ° C for 12 hours, and naturally cooled to room temperature. The above materials were pulverized by an ultrafine pulverizer, and the obtained pulverized product was dried at 100 ° C for 8 hours and passed through a 300-mesh shake sieve to obtain a C-LiFePO 4 product. Performance Testing
将实施例 1-9及比较例制备的。-ϋχΜ^Μ'γ(Χ04)η产品、 导电炭黑、 聚四氟乙烯（PTFE) 按一定的质量比例 （85: 10： 5 )均匀混合， 然后加入适量的氮甲基吡咯垸酮 （ΝΜΡ)球磨， 混合制成浆料， 将浆料均匀涂布于铝箔 （20μιη)上， 经过高温 （100Ό )真空 (-O.lMPa)干燥 4h后， 辊压制成正极片， 电极面积约 2.0.cin2， 增重 l-2mgcm— 2, 以锂片为负极， 电解液为 lmol/L L1PF6/EMC+DMC+EC (体积比 1:1:1 )， 隔膜为 0.025mm厚的聚丙烯微孔膜， 在充满 高纯 Ar (相对湿度和 02<1 % ) 的手套箱内装成 CR2025型扣式模拟电池， 使用 NEWARE电 池测试***对电池进行电性能测试， 0.2C进行充放电， 电压范围为 2.0-4.0 V。 The preparations of Examples 1-9 and Comparative Examples were prepared. -ϋ χ Μ^Μ'γ(Χ04) η product, conductive carbon black, polytetrafluoroethylene (PTFE) is uniformly mixed in a certain mass ratio (85: 10: 5), and then an appropriate amount of nitromethylpyrrolidone is added. (ΝΜΡ) ball milling, mixing into a slurry, uniformly coating the slurry on aluminum foil (20 μm), drying under high temperature (100 Ό) vacuum (-O.lMPa) for 4 hours, and rolling to form a positive electrode sheet with an electrode area of about 2.0. .cin 2 , weight gain l-2mgcm- 2 , with lithium plate as negative electrode, electrolyte is lmol/L L1PF6/EMC+DMC+EC (volume ratio 1:1:1), separator is 0.025mm thick polypropylene micro The hole film is filled with a CR2025 type button-type analog battery in a glove box filled with high-purity Ar (relative humidity and 0 2 <1%). The battery is electrically tested using the NEWARE battery test system. 0.2C is charged and discharged, and the voltage range is It is 2.0-4.0 V.
将实施例 1-9及比较例制备的材料制作成 10Ah电池， 进行倍率测试。  The materials prepared in Examples 1-9 and Comparative Examples were fabricated into a 10 Ah battery and subjected to a rate test.
Winner2000激光粒度测试仪对样品进行分析。  The Winner 2000 laser particle size tester analyzes the sample.
SSA-3500比表面积测试仪对样品进行分析。  The sample was analyzed by the SSA-3500 specific surface area tester.
BT-300粉体振实密度仪对样品进行分析。  The sample was analyzed by BT-300 powder tap density meter.
本发明实施例 1-9及比较例制备的材料的物理和化学性能检测结果见表 1及说明书附图 图 1〜图 5。  The physical and chemical properties of the materials prepared in Examples 1-9 and Comparative Examples of the present invention are shown in Table 1 and the accompanying drawings in Figures 1 to 5.
表 1  Table 1
Figure imgf000009_0001
Figure imgf000009_0001
由表 1数据可知， 根据本发明方法制得的材料导电性好， 容量高， 倍率性能好， 粒度分 布均匀且易控。  It can be seen from the data in Table 1 that the material obtained by the method of the present invention has good conductivity, high capacity, good rate performance, uniform particle size distribution and easy control.
由图 1的 SEM图谱可以看出材料颗粒均匀  It can be seen from the SEM spectrum of Figure 1 that the material particles are uniform.
由图 2的 XRD衍射图谱可以看出无杂质峰的存在。  The presence of an impurity-free peak can be seen from the XRD diffraction pattern of Fig. 2.
由图 3可以看出， 本发明采用二价铁制备的材料容量发挥更好。 由图 4可以看出， 材料循环性能很好。 As can be seen from Fig. 3, the material capacity prepared by the invention using divalent iron is better. As can be seen from Figure 4, the material cycle performance is very good.
由图 5和图 6可以看出， 采用二价铁制备的材料倍率性优于采用三价铁制备的材料。 上述实施例只是用于说明和解释本发明的内容， 不能构成对本发明范围的限制。 尽管发 明人己经对本发明做了较为详细地列举， 但是， 本领域的技术人员根据发明内容部分和实施 例所揭示的内容， 能对所描述的具体实施例做各种各样的修改或 /和补充或采用类似的方式来 替代是显然的。  It can be seen from Fig. 5 and Fig. 6 that the material magnification prepared by using ferrous iron is superior to that prepared by using ferric iron. The above-described embodiments are only intended to illustrate and explain the present invention and are not intended to limit the scope of the invention. Although the inventors have exemplified the present invention in more detail, those skilled in the art can make various modifications to the specific embodiments described, or in accordance with the disclosure of the invention. It is obvious to replace it with a supplement or in a similar way.

Claims

权利要求书 Claim
1、 一种碳包覆锂离子电池正极材料的制备方法， 其特征在于， 所述的制备方法依次包 括下述步骤： A method for preparing a carbon-coated lithium ion battery cathode material, characterized in that the preparation method comprises the following steps in sequence:
①将 Li化合物、 M化合物、 M'化合物、 X化合物和至少一种无机导电碳混合， 所得混合 物加入溶剂后做球磨处理， 球磨产物经喷雾造粒得到前驱体， 其中， 所述混合物中 Li: M: Μ': X的摩尔比 =0.95〜1.05： 0.45〜1.05： 0〜0.55： 0.95〜1.05，无机导电碳含量为 l〜20wt%; 1 a Li compound, an M compound, an M' compound, a X compound, and at least one inorganic conductive carbon are mixed, and the resulting mixture is added to a solvent to be subjected to a ball milling treatment, and the ball milled product is subjected to spray granulation to obtain a precursor, wherein the mixture is Li: M: Μ': X molar ratio = 0.95~1.05: 0.45~1.05: 0~0.55: 0.95~1.05, inorganic conductive carbon content is l~20wt%;
②气体保护氛围下，将前驱体在 200〜500°C预烧 2〜10小时，接着在 500〜800°C下二次 烧结处理 2〜24小时； 2 in a gas atmosphere, the precursor is pre-fired at 200~500 ° C for 2 to 10 hours, followed by secondary sintering at 500 to 800 ° C for 2 to 24 hours;
③待步骤②所得产物冷却至室温后做粉碎即可得到符合通式
Figure imgf000011_0001
的材料， 其中， 0<x≤2， 0≤y≤0.5、 l≤n≤1.5， M是过渡金属元素， M'选自 Mg、 Ti、 Cr、 V或 Al 中至少一种， X选自 S、 P或 Si。 3 After the product obtained in step 2 is cooled to room temperature, it is pulverized to obtain a general formula.
Figure imgf000011_0001
The material, wherein, 0 < x ≤ 2, 0 ≤ y ≤ 0.5, l ≤ n ≤ 1.5, M is a transition metal element, and M' is at least one selected from the group consisting of Mg, Ti, Cr, V or Al, and X is selected from the group consisting of S, P or Si.
2、 如权利要求 1所述的制备方法， 其特征在于， 所述步骤①中的 M化合物选自铁、 锰、 钴或镍盐中一种。  The method according to claim 1, wherein the compound of the M in the step 1 is one selected from the group consisting of iron, manganese, cobalt or nickel salts.
3、如权利要求 2所述的制备方法， 其特征在于， 所述铁盐指二价铁盐， 选用草酸铁盐或 醋酸铁盐。  The method according to claim 2, wherein the iron salt is a divalent iron salt, and an iron oxalate salt or an iron acetate salt is used.
4、如权利要求 1所述的制备方法， 其特征在于， 所述步骤①中的 Li化合物选自碳酸锂、 氢氧化锂、 磷酸二氢锂、 醋酸锂或硝酸锂中至少一种。  The method according to claim 1, wherein the Li compound in the step 1 is at least one selected from the group consisting of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, lithium acetate or lithium nitrate.
5、如权利要求 1所述的制备方法， 其特征在于， 所述步骤①中的无机导电碳选自天然石 墨、 人造石墨微粉、 碳黑颗粒、 乙炔黑颗粒、 碳纳米管、 纳米碳纤维或有机物高温热解后所 得到的无机碳中的至少一种。  The method according to claim 1, wherein the inorganic conductive carbon in the step 1 is selected from the group consisting of natural graphite, artificial graphite fine powder, carbon black particles, acetylene black particles, carbon nanotubes, nano carbon fibers or organic substances. At least one of the inorganic carbons obtained after pyrolysis at a high temperature.
6、如权利要求 1所述的制备方法， 其特征在于， 所述步骤①中的溶剂选自去离子水、 乙 醇、 乙二醇、 丙醇、 异丙醇、 正丁醇、 甘油或乙二胺中的至少一种。  The preparation method according to claim 1, wherein the solvent in the step 1 is selected from the group consisting of deionized water, ethanol, ethylene glycol, propanol, isopropanol, n-butanol, glycerin or ethylene. At least one of the amines.
7、如权利要求 1所述的制备方法， 其特征在于， 所述步骤②中的气体为氢气、氮气或氩 气中的至少一种。  The preparation method according to claim 1, wherein the gas in the step 2 is at least one of hydrogen, nitrogen or argon.
8、 如权利要求 1所述的制备方法， 其特征在于， 所述步骤②中预烧为在 300〜500°C下 处理 4〜8小时。  8. The preparation method according to claim 1, wherein the calcination in the step 2 is carried out at 300 to 500 ° C for 4 to 8 hours.
9、 如权利要求 1所述的制备方法， 其特征在于， 所述步骤②中二次烧结为在 550〜780 °C下处理 5-20小时。  9. The preparation method according to claim 1, wherein the second sintering in the step 2 is carried out at 550 to 780 ° C for 5 to 20 hours.
10、如权利要求 1所述的制备方法， 其特征在于， 所述步骤③中的粉碎采用超微粉碎机、 气流粉碎机、 机械式粉碎机或复合粉碎机。  The preparation method according to claim 1, wherein the pulverization in the step 3 is performed by an ultrafine pulverizer, a jet mill, a mechanical pulverizer or a composite pulverizer.
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