WO2012062110A1 - Preparing method of composite lithium iron phosphate/carbon for lithium ion battery - Google Patents

Preparing method of composite lithium iron phosphate/carbon for lithium ion battery Download PDF

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WO2012062110A1
WO2012062110A1 PCT/CN2011/075932 CN2011075932W WO2012062110A1 WO 2012062110 A1 WO2012062110 A1 WO 2012062110A1 CN 2011075932 W CN2011075932 W CN 2011075932W WO 2012062110 A1 WO2012062110 A1 WO 2012062110A1
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iron phosphate
lithium iron
graphene
carbon
ion battery
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PCT/CN2011/075932
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French (fr)
Chinese (zh)
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朱杰
杜振山
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河北力滔电池材料有限公司
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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
    • H01M4/13—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 ion batteries, and particularly relates to a preparation method of a lithium ion battery composite material lithium iron phosphate/carbon. Background technique
  • the synthesis method of lithium iron phosphate material is mainly divided into a solid phase method and a liquid phase method.
  • the solid phase method mainly utilizes iron salt, lithium salt and phosphate to synthesize lithium iron phosphate at high temperature sintering.
  • a soluble iron salt, a lithium salt, and a phosphoric acid salt are dissolved in a solvent, and lithium iron phosphate or a precursor thereof is prepared by ion reaction, and then a high-temperature sintering is performed to obtain a finished product.
  • the solid phase reaction is simple, the raw materials are easy to handle, and the yield is high, but the morphology of the raw materials is not easy to control, and the tap density and compaction density of the product are low.
  • the invention patents CN101200289, CN1762798, CN101140985, etc. all adopt a solid phase synthesis process route.
  • Some new synthetic methods such as microwave synthesis (CN101172597, CN101807692A) and ultrasonic coprecipitation (CN101800311A), can be attributed to solid phase synthesis.
  • the liquid phase method requires the use of a reactor for pre-treatment, and also requires drying, filtration, etc., and the process is complicated.
  • the sphericity of the product is generally good, the tap density is high, and the capacity and high rate performance are excellent.
  • the invention patents CN101172599, CN101047242, and CN101121509 all adopt the above process route.
  • iron phosphate materials are coated with a conductive carbon layer. It is actually a lithium iron phosphate/carbon composite. Only the lithium iron phosphate material coated with carbon can exert its electrochemical performance normally. However, the carbon added by the general process is loosely distributed and loosely distributed among the lithium iron phosphate particles, which seriously reduces the bulk density of the lithium iron phosphate material, making its tap density much lower than its theoretical density, and affecting the subsequent The compact density of the pole piece. How to minimize the carbon content in the cathode material without reducing the carbon coating effect of the material, without reducing the conductivity, electrochemical capacity and cycle performance, is a concern of materials research. Summary of the invention
  • the present invention provides a method for preparing a lithium ion battery composite lithium iron phosphate/carbon in order to solve the problems existing in the prior art.
  • the object of the present invention is to provide a lithium ion battery composite lithium iron phosphate/carbon preparation method which has the advantages of simple process, convenient operation, excellent material performance, high electrical conductivity, high bulk density and high compaction density, and stable product quality.
  • Graphene is extremely thin, very soft and has excellent flexibility. It is an ideal material for coating lithium iron phosphate. It is conceivable that the lithium iron phosphate material coated with an appropriate amount of graphene has a small carbon content, but the electrical conductivity of the material is lowered. At the same time, since the graphene is tightly coated on the surface of the lithium iron phosphate particles, there is no loose carbon between the grains, and the density of the material is greatly increased.
  • the invention provides a preparation and synthesis method of a lithium iron phosphate/carbon composite material, wherein carbon is tightly coated on the surface of lithium iron phosphate in the form of graphene, thereby reducing the carbon content in the positive electrode material to less than 1% (in general materials) Containing more than 3% carbon), the material is densely distributed, increasing the density of lithium iron phosphate material.
  • the process route adopted by the invention is as follows: Firstly, a graphene stable dispersion aqueous solution system is prepared by using a thermal differential layer stripping technique, and then the pure lithium iron phosphate material is treated with the solution to adsorb the graphene on the surface of the lithium iron phosphate particles, and then subjected to heat treatment. The combination of graphene and lithium iron phosphate provides the desired lithium iron phosphate/carbon composite.
  • the preparation method of the lithium ion battery composite material lithium iron phosphate/carbon of the invention adopts the following technical solutions:
  • a lithium ion battery composite material lithium iron phosphate / carbon preparation method, coated with lithium iron phosphate, characterized by: composite lithium iron phosphate / carbon preparation process includes:
  • Preparing a suspended graphene dispersed aqueous solution system preparing a suspended graphene dispersed aqueous solution system by using a hot differential layer stripping method; pulverizing the natural graphite to a particle size of 1-5 micrometers, and adding it to steamed water or purified water. Adding 0.1-5% of the surfactant, under shear and stirring, the temperature of the seal is raised to 180-250 ° C, stirred for 2-6 hours, and the temperature is lowered;
  • the preparation method of the lithium ion battery composite material lithium iron phosphate/carbon of the invention can also adopt the following technical measures:
  • the preparation method of the lithium ion battery composite material lithium iron phosphate/carbon characterized in that: the surfactant is phenylenediamine , polyvinylpyrrolidone, alkylphenol ethoxylates, and the like. It can be peeled off between the graphite layers in the hydrothermal state and stabilizes the graphene/water system.
  • the preparation method of the lithium ion battery composite material lithium iron phosphate/carbon is characterized in that: the coupling agent is Y-mercaptopropyltrimethoxysilane, methyl isobutyl ketone decyl silane, vinyl triethoxy Silane and the like. It can adhere to the surface of lithium iron phosphate and is easily crosslinked with graphene.
  • the method for preparing a lithium ion battery composite lithium iron phosphate/carbon is characterized in that: the weight percentage concentration of graphene in the graphene-dispersed aqueous solution is ⁇ - ⁇ %.
  • the method for preparing a lithium ion battery composite material lithium iron phosphate/carbon characterized in that: adding graphene dispersion After the aqueous solution, the mixture was stirred at 20 to 40 ° C for 4 to 10 hours, and then allowed to stand for 12 to 36 hours, followed by stirring.
  • the lithium ion battery composite material lithium iron phosphate / carbon preparation method is characterized in that: when the solid powder is dried by vacuum, the vacuum drying temperature is 120-150 ° C.
  • Lithium ion battery composite material lithium iron phosphate / carbon preparation method due to the adoption of the novel technical solution of the present invention, compared with the prior art, the iron phosphate/carbon material prepared by the invention, the graphene is completely nanometerly distributed in the phosphoric acid
  • the surface of the iron-lithium material forms a surface carbon layer with extremely high electrical conductivity and does not produce a loose bulk carbon layer.
  • the bulk density and compaction density of the lithium iron phosphate cathode material are effectively increased. ⁇
  • the measured, the carbon content of the material was reduced to 0. 8-1%, the body conductivity was maintained at 0. 01S / cm.
  • the tap density is increased to 1. 8g/cm3, the 0.
  • 1C capacity is 155mAh/g
  • the compact density of the capacity pole piece is increased from 2. 2 g/cm3 to 2. 6-2. 7 g/cm3.
  • the overall performance of the lithium iron phosphate material has been greatly improved.
  • the invention has the advantages of simple process, convenient operation, excellent material performance, high electrical conductivity, high bulk density and compact density, and stable product quality. detailed description
  • a method for preparing a lithium ion battery composite lithium iron phosphate/carbon firstly preparing a stable suspended graphene-water system.
  • the concentration of graphene in the system is 1%.
  • the natural graphite is first pulverized to an average particle size of about 1 micrometer, and then added to the distilled water, and 0.1% of the surfactant phenylenediamine is added, and the temperature is raised to 180 ° C under high shear agitation. Stirring was continued for 6 hours under high temperature and high pressure, and the temperature was lowered to obtain a stable suspended graphene-water system.
  • a method for preparing a lithium ion battery composite lithium iron phosphate/carbon firstly preparing a stable suspended graphene-water system.
  • the concentration of graphene in the system is generally 10%.
  • the natural graphite was first pulverized to an average particle size of 5 ⁇ m, and then added to purified water, and 5% of a surfactant polyvinylpyrrolidone was added, and the temperature was raised to 250 ° C under high-speed shear stirring. Stirring was continued for 2 hours under high temperature and high pressure, and the temperature was lowered to obtain a stable suspended graphene-water system.
  • a method for preparing a lithium ion battery composite lithium iron phosphate/carbon firstly preparing a stable suspended graphene-water system.
  • the concentration of graphene in the system was 2%.
  • the natural graphite was first pulverized to an average particle diameter of 2 ⁇ m, and then added to pure water, and 1% of a surfactant alkylphenol ethoxylate was added, and the temperature was raised to 200 ° C under high-speed shear stirring. Stirring was continued for 4 hours under high temperature and high pressure, and the temperature was lowered to obtain a stable suspended graphene-water system.
  • the lithium iron phosphate/carbon composite material of the lithium ion battery prepared by the invention has the graphene completely distributed on the surface of the lithium iron phosphate material, forming a surface carbon layer having extremely high conductivity, and effectively increasing the lithium iron phosphate positive electrode.
  • the bulk density and compaction density of the material, the lithium iron phosphate/carbon composite material has the positive positive effects described.

Abstract

A preparing method of a composite lithium iron phosphate/carbon for a lithium ion battery is provided. The method includes steps as follows: 1) preparing a suspension graphene-scattered aqueous solution system: crushing a graphite to 1-5μm, adding a distilled water or a purified water, adding 0.1-5% a surfactant under the stirring condition, increasing the temperature to 180-250℃ under the sealing condition, stirring for 2-6 hours, and cooling; 2) crushing a lithium iron phosphate to 1-5μm, adding the distilled water or the purified water, adding 0.01-1% a coupling agent under stirring condition, uniformly stirring, adding the graphene-scattered aqueous solution, stirring and filtering; 3) vacuum-drying solid powder obtained by filtering, sintering for 2-12 hours, and obtaining the graphene-coated lithium iron phosphate positive material. The method has simple technique, and the material prepared by the method has the advantages of excellent performance, high conductive ability, high stacking and compaction intensity and so on.

Description

一种锂离子电池复合材料磷酸铁锂 /碳的制备方法 技术领域  Method for preparing lithium ion battery composite material lithium iron phosphate/carbon
本发明属于锂离子电池技术领域， 特别是涉及一种锂离子电池复合材料磷酸铁锂 / 碳的制备方法。 背景技术  The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a lithium ion battery composite material lithium iron phosphate/carbon. Background technique
目前，磷酸铁锂材料的合成方法主要分成固相法和液相法。固相法主要是利用铁盐、 锂盐和磷酸盐， 在高温烧结实现磷酸铁锂的合成。 液相法是将可溶性铁盐、 锂盐和磷酸 盐溶解在溶剂中， 利用离子反应制成磷酸铁锂或其前驱体， 再通过高温烧结制成成品。 固相法反应简便， 原料容易处理， 产率高， 但是原料形貌不容易控制， 产品振实密度和 压实密度低。 例如， 发明专利 CN101200289、 CN1762798、 CN101140985等都是采用固相 合成工艺路线。 一些新的合成方法， 如微波合成法 （CN101172597、 CN101807692A) 、 超声共沉淀法（CN101800311A) ， 都可以归结到固相合成法中。 而液相法需要利用反应 釜进行前期处理， 同时也需要干燥、 过滤等过程， 工艺比较复杂。 但是产品球形度一般 较好， 振实密度较高， 容量和高倍率性能出色。 发明专利 CN101172599、 CN101047242, CN101121509都是采用以上工艺路线。  At present, the synthesis method of lithium iron phosphate material is mainly divided into a solid phase method and a liquid phase method. The solid phase method mainly utilizes iron salt, lithium salt and phosphate to synthesize lithium iron phosphate at high temperature sintering. In the liquid phase method, a soluble iron salt, a lithium salt, and a phosphoric acid salt are dissolved in a solvent, and lithium iron phosphate or a precursor thereof is prepared by ion reaction, and then a high-temperature sintering is performed to obtain a finished product. The solid phase reaction is simple, the raw materials are easy to handle, and the yield is high, but the morphology of the raw materials is not easy to control, and the tap density and compaction density of the product are low. For example, the invention patents CN101200289, CN1762798, CN101140985, etc. all adopt a solid phase synthesis process route. Some new synthetic methods, such as microwave synthesis (CN101172597, CN101807692A) and ultrasonic coprecipitation (CN101800311A), can be attributed to solid phase synthesis. The liquid phase method requires the use of a reactor for pre-treatment, and also requires drying, filtration, etc., and the process is complicated. However, the sphericity of the product is generally good, the tap density is high, and the capacity and high rate performance are excellent. The invention patents CN101172599, CN101047242, and CN101121509 all adopt the above process route.
磷酸铁材料的成功应用在于其表面包覆有导电碳层。 实际是一种磷酸铁锂 /碳复合 材料。 只有包覆了碳的磷酸铁锂材料才能正常发挥其电化学性能。 但是， 一般的工艺加 入的碳由于质地疏松， 且在磷酸铁锂颗粒间呈松散分布， 严重降低了磷酸铁锂材料的堆 积密度， 使其振实密度大大低于其理论密度， 也影响了随后极片的压实密度。 如何尽量 减少正极材料中的碳含量， 同时又不降低材料的碳包覆效果， 从而不降低电导率、 电化 学容量和循环性能， 是材料研究的关注问题。 发明内容  A successful application of iron phosphate materials is that their surfaces are coated with a conductive carbon layer. It is actually a lithium iron phosphate/carbon composite. Only the lithium iron phosphate material coated with carbon can exert its electrochemical performance normally. However, the carbon added by the general process is loosely distributed and loosely distributed among the lithium iron phosphate particles, which seriously reduces the bulk density of the lithium iron phosphate material, making its tap density much lower than its theoretical density, and affecting the subsequent The compact density of the pole piece. How to minimize the carbon content in the cathode material without reducing the carbon coating effect of the material, without reducing the conductivity, electrochemical capacity and cycle performance, is a concern of materials research. Summary of the invention
本发明为解决现有技术存在的问题， 提供了一种锂离子电池复合材料磷酸铁锂 /碳 的制备方法。  The present invention provides a method for preparing a lithium ion battery composite lithium iron phosphate/carbon in order to solve the problems existing in the prior art.
本发明目的是提供一种具有工艺简单， 操作方便， 材料性能优良， 导电能力高， 堆 积密度和压实密度高， 产品质量稳定等优点的锂离子电池复合材料磷酸铁锂 /碳的制备 方法。  SUMMARY OF THE INVENTION The object of the present invention is to provide a lithium ion battery composite lithium iron phosphate/carbon preparation method which has the advantages of simple process, convenient operation, excellent material performance, high electrical conductivity, high bulk density and high compaction density, and stable product quality.
研究表明， 减少碳含量而不降低磷酸铁锂 /碳体系的电导率， 只能通过引入具有更 高导电能力的碳材料来实现。在实际生产中，合成温度越高，碳材料的石墨化程度越高， 导电性也越好。但高的合成温度会造成磷酸铁锂材料的晶粒过大，锂离子扩散距离增加， 使材料放电容量降低。 石墨烯材料的出现， 为磷酸铁锂 /碳材料的进步提出了理论依据。 石墨烯是一种二 维网状结构的碳材料， 具有 sp2杂化轨道， 由于具有显著的量子隧道效应， 其电导率是 铜的 100倍。 石墨烯极薄， 又非常柔软， 挠曲性极好， 是用于磷酸铁锂材料包覆的理想 材料。 可以设想， 利用适量石墨烯包覆的磷酸铁锂材料， 碳含量很少， 但材料的电导率 并降低。 同时由于石墨烯紧紧包覆在磷酸铁锂颗粒表面， 晶粒间不会有松散碳， 材料的 密度会大幅度提高。 Studies have shown that reducing carbon content without lowering the conductivity of lithium iron phosphate/carbon systems can only be achieved by introducing carbon materials with higher electrical conductivity. In actual production, the higher the synthesis temperature, the higher the degree of graphitization of the carbon material and the better the conductivity. However, the high synthesis temperature causes the crystal grains of the lithium iron phosphate material to be excessively large, and the lithium ion diffusion distance is increased to lower the discharge capacity of the material. The appearance of graphene materials provides a theoretical basis for the advancement of lithium iron phosphate/carbon materials. Graphene is a two-dimensional network of carbon materials with sp2 hybrid orbitals. Its conductivity is 100 times that of copper due to its remarkable quantum tunneling effect. Graphene is extremely thin, very soft and has excellent flexibility. It is an ideal material for coating lithium iron phosphate. It is conceivable that the lithium iron phosphate material coated with an appropriate amount of graphene has a small carbon content, but the electrical conductivity of the material is lowered. At the same time, since the graphene is tightly coated on the surface of the lithium iron phosphate particles, there is no loose carbon between the grains, and the density of the material is greatly increased.
本发明提供一种磷酸铁锂 /碳复合材料的制备合成方法， 其中碳以石墨烯形式紧紧 包覆在磷酸铁锂表面， 从而使正极材料中的碳含量减少到 1%以下 （一般材料中含有 3% 以上碳） ， 材料分布致密， 增加了磷酸铁锂材料的致密度。  The invention provides a preparation and synthesis method of a lithium iron phosphate/carbon composite material, wherein carbon is tightly coated on the surface of lithium iron phosphate in the form of graphene, thereby reducing the carbon content in the positive electrode material to less than 1% (in general materials) Containing more than 3% carbon), the material is densely distributed, increasing the density of lithium iron phosphate material.
本发明所采用的工艺路线是： 首先用水热差层剥离技术制备石墨烯稳定分散的水溶 液体系， 然后用该溶液处理纯磷酸铁锂材料， 使石墨烯吸附在磷酸铁锂颗粒表面， 然后 经过热处理使石墨烯和磷酸铁锂紧密结合， 即制成了所需要的磷酸铁锂 /碳复合材料。  The process route adopted by the invention is as follows: Firstly, a graphene stable dispersion aqueous solution system is prepared by using a thermal differential layer stripping technique, and then the pure lithium iron phosphate material is treated with the solution to adsorb the graphene on the surface of the lithium iron phosphate particles, and then subjected to heat treatment. The combination of graphene and lithium iron phosphate provides the desired lithium iron phosphate/carbon composite.
本发明锂离子电池复合材料磷酸铁锂 /碳的制备方法采用如下技术方案：  The preparation method of the lithium ion battery composite material lithium iron phosphate/carbon of the invention adopts the following technical solutions:
一种锂离子电池复合材料磷酸铁锂 /碳的制备方法， 用碳包覆磷酸铁锂， 其特点是： 复合材料磷酸铁锂 /碳的制备过程包括：  A lithium ion battery composite material lithium iron phosphate / carbon preparation method, coated with lithium iron phosphate, characterized by: composite lithium iron phosphate / carbon preparation process includes:
1、 制备悬浮的石墨烯分散的水溶液体系： 用水热差层剥离方法制备悬浮的石墨烯 分散的水溶液体系； 将天然石墨粉碎到 1-5微米的粒径， 加入到蒸熘水或纯净水中， 加 入 0. 1-5%的表面活性剂， 在剪切搅拌状态下， 密封升温到 180-250°C， 搅拌 2_6小时， 降温；  1. Preparing a suspended graphene dispersed aqueous solution system: preparing a suspended graphene dispersed aqueous solution system by using a hot differential layer stripping method; pulverizing the natural graphite to a particle size of 1-5 micrometers, and adding it to steamed water or purified water. Adding 0.1-5% of the surfactant, under shear and stirring, the temperature of the seal is raised to 180-250 ° C, stirred for 2-6 hours, and the temperature is lowered;
2、 用上述溶液处理纯磷酸铁锂材料： 将磷酸铁锂粉碎到粒径 1-5微米， 按照磷酸 铁锂： 水 = 1 : 1-10的比例加入蒸熘水或纯净水； 搅拌状态下， 加入总重量 0. 01-1%的 偶联剂， 搅拌均匀； 加入上述石墨烯分散的水溶液， 搅拌， 过滤；  2. Treat the pure lithium iron phosphate material with the above solution: pulverize the lithium iron phosphate to a particle size of 1-5 μm, and add steamed water or purified water according to the ratio of lithium iron phosphate: water = 1: 1-10; , adding a total weight of 0. 01-1% of the coupling agent, stirring evenly; adding the above graphene dispersed aqueous solution, stirring, filtering;
3、热处理石墨烯和磷酸铁锂材料： 过滤得到的固体粉料在真空烘干， 在 250-350°C 氮气或氩气气氛下煅烧 2-12小时， 得到被石墨烯包覆的磷酸铁锂正极材料。  3. Heat treatment of graphene and lithium iron phosphate material: The solid powder obtained by filtration is vacuum dried, calcined at 250-350 ° C under nitrogen or argon atmosphere for 2-12 hours to obtain graphene-coated lithium iron phosphate. Cathode material.
本发明锂离子电池复合材料磷酸铁锂 /碳的制备方法还可以采用如下技术措施： 所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法， 其特点是： 表面活性剂为苯 二胺、 聚乙烯基吡咯烷酮、 烷基酚聚氧乙烯醚等。 可以在水热状态进入石墨层间起到剥 离作用， 并使石墨烯 /水体系稳定。  The preparation method of the lithium ion battery composite material lithium iron phosphate/carbon of the invention can also adopt the following technical measures: The preparation method of the lithium ion battery composite material lithium iron phosphate/carbon, characterized in that: the surfactant is phenylenediamine , polyvinylpyrrolidone, alkylphenol ethoxylates, and the like. It can be peeled off between the graphite layers in the hydrothermal state and stabilizes the graphene/water system.
所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法， 其特点是： 偶联剂为 Y -巯丙 基三甲氧基硅烷、 甲基异丁基酮肟基硅烷、 乙烯基三乙氧基硅烷等。 可以附着在磷酸铁 锂表面， 易于与石墨烯交联。  The preparation method of the lithium ion battery composite material lithium iron phosphate/carbon is characterized in that: the coupling agent is Y-mercaptopropyltrimethoxysilane, methyl isobutyl ketone decyl silane, vinyl triethoxy Silane and the like. It can adhere to the surface of lithium iron phosphate and is easily crosslinked with graphene.
所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法， 其特点是： 石墨烯分散的水 溶液中石墨烯的重量百分比浓度为 ι-ιο%。  The method for preparing a lithium ion battery composite lithium iron phosphate/carbon is characterized in that: the weight percentage concentration of graphene in the graphene-dispersed aqueous solution is ι-ιο%.
所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法， 其特点是： 加入石墨烯分散 的水溶液后， 在 20-40°C条件下搅拌 4-10小时， 然后静置 12-36小时， 再搅拌。 The method for preparing a lithium ion battery composite material lithium iron phosphate/carbon, characterized in that: adding graphene dispersion After the aqueous solution, the mixture was stirred at 20 to 40 ° C for 4 to 10 hours, and then allowed to stand for 12 to 36 hours, followed by stirring.
所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法， 其特点是： 固体粉料真空烘 干时， 真空烘干温度为 120-150°C。  The lithium ion battery composite material lithium iron phosphate / carbon preparation method is characterized in that: when the solid powder is dried by vacuum, the vacuum drying temperature is 120-150 ° C.
本发明具有的优点和积极效果：  The invention has the advantages and positive effects:
锂离子电池复合材料磷酸铁锂 /碳的制备方法， 由于采用了本发明全新的技术方案， 与现有技术相比， 本发明制得的磷酸铁 /碳材料， 石墨烯完整纳米地分布在磷酸铁锂材 料表面， 形成了具有极高导电能力的表面碳层， 并不会产生疏松大块碳层。 有效地增加 了磷酸铁锂正极材料的堆积密度和压实密度。 据实验测定， 材料中的碳含量降低到 0. 8-1%，体电导率维持在 0. 01S/cm。振实密度提高到 1. 8g/cm3, 0. 1C容量达到 155mAh/g， 容量极片的压实密度从 2. 2 g/cm3提高到 2. 6-2. 7 g/cm3。 大大改善了磷酸铁锂材料的 综合性能。 本发明具有工艺简单， 操作方便， 材料性能优良， 导电能力高， 堆积密度和 压实密度高， 产品质量稳定等优点。 具体实施方式  Lithium ion battery composite material lithium iron phosphate / carbon preparation method, due to the adoption of the novel technical solution of the present invention, compared with the prior art, the iron phosphate/carbon material prepared by the invention, the graphene is completely nanometerly distributed in the phosphoric acid The surface of the iron-lithium material forms a surface carbon layer with extremely high electrical conductivity and does not produce a loose bulk carbon layer. The bulk density and compaction density of the lithium iron phosphate cathode material are effectively increased.约。 The measured, the carbon content of the material was reduced to 0. 8-1%, the body conductivity was maintained at 0. 01S / cm. The tap density is increased to 1. 8g/cm3, the 0. 1C capacity is 155mAh/g, and the compact density of the capacity pole piece is increased from 2. 2 g/cm3 to 2. 6-2. 7 g/cm3. The overall performance of the lithium iron phosphate material has been greatly improved. The invention has the advantages of simple process, convenient operation, excellent material performance, high electrical conductivity, high bulk density and compact density, and stable product quality. detailed description
为能进一步了解本发明的技术内容、 特点及功效， 兹列举以下实例， 并详细说明如 下：  In order to further understand the technical content, features and effects of the present invention, the following examples are listed, and the following details are as follows:
实施例 1  Example 1
锂离子电池复合材料磷酸铁锂 /碳的制备方法， 首先制备稳定悬浮的石墨烯 -水体 系。体系中石墨烯的浓度 1%。先将天然石墨粉碎到 1微米左右的平均粒径， 然后加入到 蒸熘水中，加入 0. 1%的表面活性剂苯二胺，在高速剪切搅拌状态下，密封升温到 180°C。 在高温高压下继续搅拌 6小时， 降温， 制得稳定悬浮的石墨烯-水体系。  A method for preparing a lithium ion battery composite lithium iron phosphate/carbon, firstly preparing a stable suspended graphene-water system. The concentration of graphene in the system is 1%. The natural graphite is first pulverized to an average particle size of about 1 micrometer, and then added to the distilled water, and 0.1% of the surfactant phenylenediamine is added, and the temperature is raised to 180 ° C under high shear agitation. Stirring was continued for 6 hours under high temperature and high pressure, and the temperature was lowered to obtain a stable suspended graphene-water system.
将纯的磷酸铁锂粉碎到平均粒径 1微米， 按照磷酸铁锂： 水 = 1： 1的比例加入纯 净水。搅拌状态下，加入总重量 0. 01%重量的偶联剂 Y -巯丙基三甲氧基硅烷用以增强磷 酸铁锂材料对石墨烯的吸附能力， 搅拌均匀。将分散好的石墨烯溶液缓慢加入， 在 20°C 条件下搅拌 4小时。 静置 12小时。 再次搅拌 1小时， 将液体过滤， 得到的固体粉料在 真空条件下 120°C烘干去掉水分， 然后在 250°C氮气氛下煅烧 2小时， 得到被石墨烯包 覆的磷酸铁锂正极材料。  Pure lithium iron phosphate was pulverized to an average particle diameter of 1 μm, and pure water was added in a ratio of lithium iron phosphate: water = 1:1. Under stirring, a total weight of 0.01% by weight of the coupling agent Y-mercaptopropyltrimethoxysilane was used to enhance the adsorption capacity of the lithium iron phosphate material for graphene, and the stirring was uniform. The dispersed graphene solution was slowly added and stirred at 20 ° C for 4 hours. Allow to stand for 12 hours. After stirring for another hour, the liquid was filtered, and the obtained solid powder was dried under vacuum at 120 ° C to remove water, and then calcined under a nitrogen atmosphere at 250 ° C for 2 hours to obtain a graphene-coated lithium iron phosphate cathode material. .
实施例 2  Example 2
锂离子电池复合材料磷酸铁锂 /碳的制备方法， 首先制备稳定悬浮的石墨烯 -水体 系。 体系中石墨烯的浓度一般在 10%。 先将天然石墨粉碎到 5微米的平均粒径， 然后加 入到纯净水中， 加入 5%的表面活性剂聚乙烯基吡咯烷酮， 在高速剪切搅拌状态下， 密封 升温到 250°C。 在高温高压下继续搅拌 2小时， 降温， 制得稳定悬浮的石墨烯-水体系。  A method for preparing a lithium ion battery composite lithium iron phosphate/carbon, firstly preparing a stable suspended graphene-water system. The concentration of graphene in the system is generally 10%. The natural graphite was first pulverized to an average particle size of 5 μm, and then added to purified water, and 5% of a surfactant polyvinylpyrrolidone was added, and the temperature was raised to 250 ° C under high-speed shear stirring. Stirring was continued for 2 hours under high temperature and high pressure, and the temperature was lowered to obtain a stable suspended graphene-water system.
将纯的磷酸铁锂粉碎到平均粒径 5微米， 按照磷酸铁锂： 水 = 1 : 10的比例加入纯 净水。搅拌状态下，加入总重量 1%重量的偶联剂甲基异丁基酮肟基硅烷用以增强磷酸铁 锂材料对石墨烯的吸附能力， 搅拌均匀。将分散好的石墨烯溶液缓慢加入， 在 40°C条件 下搅拌 10小时。 静置 36小时。 再次搅拌 2小时， 将液体过滤， 得到的固体粉料在真空 条件下 150°C烘干去掉水分， 然后在 350°C氩气气氛下煅烧 12小时， 得到被石墨烯包覆 的磷酸铁锂正极材料。 Pure lithium iron phosphate was pulverized to an average particle diameter of 5 μm, and purified water was added in a ratio of lithium iron phosphate: water = 1:10. Under stirring, a total weight of 1% by weight of the coupling agent methyl isobutyl ketone silane is added to enhance the iron phosphate. The adsorption capacity of lithium material for graphene is evenly stirred. The dispersed graphene solution was slowly added and stirred at 40 ° C for 10 hours. Allow to stand for 36 hours. After stirring for another 2 hours, the liquid was filtered, and the obtained solid powder was dried under vacuum at 150 ° C to remove water, and then calcined under an argon atmosphere at 350 ° C for 12 hours to obtain a graphene-coated lithium iron phosphate positive electrode. material.
实施例 3  Example 3
锂离子电池复合材料磷酸铁锂 /碳的制备方法， 首先制备稳定悬浮的石墨烯 -水体 系。体系中石墨烯的浓度为 2%。先将天然石墨粉碎到 2微米的平均粒径， 然后加入到纯 净水中， 加入 1%的表面活性剂烷基酚聚氧乙烯醚， 在高速剪切搅拌状态下， 密封升温到 200°C。 在高温高压下继续搅拌 4小时， 降温， 制得稳定悬浮的石墨烯-水体系。  A method for preparing a lithium ion battery composite lithium iron phosphate/carbon, firstly preparing a stable suspended graphene-water system. The concentration of graphene in the system was 2%. The natural graphite was first pulverized to an average particle diameter of 2 μm, and then added to pure water, and 1% of a surfactant alkylphenol ethoxylate was added, and the temperature was raised to 200 ° C under high-speed shear stirring. Stirring was continued for 4 hours under high temperature and high pressure, and the temperature was lowered to obtain a stable suspended graphene-water system.
将纯的磷酸铁锂粉碎到平均粒径 3微米， 按照磷酸铁锂： 水 = 1： 5的比例加入纯 净水。搅拌状态下，加入总重量 0. 1%重量的偶联剂乙烯基三乙氧基硅烷用以增强磷酸铁 锂材料对石墨烯的吸附能力， 搅拌均匀。将分散好的石墨烯溶液缓慢加入， 在 25°C条件 下搅拌 6小时。 静置 24小时。 再次搅拌 1. 5小时， 将液体过滤， 得到的固体粉料在真 空条件下 135度烘干去掉水分， 然后在 300°C氩气气氛下煅烧 8小时， 得到被石墨烯包 覆的磷酸铁锂正极材料。  Pure lithium iron phosphate was pulverized to an average particle diameter of 3 μm, and pure water was added in a proportion of lithium iron phosphate: water = 1:5. Under stirring, a total weight of 0.1% by weight of the coupling agent vinyltriethoxysilane was added to enhance the adsorption capacity of the lithium iron phosphate material for graphene, and the stirring was uniform. The dispersed graphene solution was slowly added and stirred at 25 ° C for 6 hours. Allow to stand for 24 hours. After stirring for 1.5 hours, the liquid was filtered, and the obtained solid powder was dried at 135 degree under vacuum to remove water, and then calcined under an argon atmosphere at 300 ° C for 8 hours to obtain graphene-coated lithium iron phosphate. Cathode material.
本发明制得的锂离子电池磷酸铁锂 /碳复合材料， 其石墨烯完整纳米地分布在磷酸 铁锂材料表面， 形成了具有极高导电能力的表面碳层， 有效地增加了磷酸铁锂正极材料 的堆积密度和压实密度， 磷酸铁锂 /碳复合材料的具有所述的积极优良效果。  The lithium iron phosphate/carbon composite material of the lithium ion battery prepared by the invention has the graphene completely distributed on the surface of the lithium iron phosphate material, forming a surface carbon layer having extremely high conductivity, and effectively increasing the lithium iron phosphate positive electrode. The bulk density and compaction density of the material, the lithium iron phosphate/carbon composite material has the positive positive effects described.

Claims

权利要求书 Claim
1. 一种锂离子电池复合材料磷酸铁锂 /碳的制备方法， 用碳包覆磷酸铁锂， 其特征 是： 复合材料磷酸铁锂 /碳的制备过程包括： A lithium ion battery composite material lithium iron phosphate / carbon preparation method, coated with lithium iron phosphate, characterized by: composite lithium iron phosphate / carbon preparation process includes:
1 ) 、 制备悬浮的石墨烯分散的水溶液体系： 用水热差层剥离方法制备悬浮的石墨 烯分散的水溶液体系； 将天然石墨粉碎到 1-5微米的粒径， 加入到蒸熘水或纯净水中， 加入 0.1-5%的表面活性剂， 在剪切搅拌状态下， 密封升温到 180-250°C， 搅拌 2-6小时， 降温；  1) preparing a suspended graphene dispersed aqueous solution system: preparing a suspended graphene dispersed aqueous solution system by using a hydrothermal difference layer stripping method; pulverizing natural graphite to a particle size of 1-5 micrometers, adding to distilled water or purified water , adding 0.1-5% of the surfactant, under the condition of shear stirring, the temperature is raised to 180-250 ° C, stirred for 2-6 hours, and the temperature is lowered;
2) 、 用上述溶液处理纯磷酸铁锂材料： 将磷酸铁锂粉碎到粒径 1-5 微米， 按照磷 酸铁锂： 水 = 1： 1-10的比例加入蒸熘水或纯净水； 搅拌状态下， 加入总重量 0.01-1% 的偶联剂， 搅拌均匀； 加入上述石墨烯分散的水溶液， 搅拌， 过滤；  2), treating the pure lithium iron phosphate material with the above solution: crushing lithium iron phosphate to a particle size of 1-5 micrometers, adding distilled water or purified water according to the ratio of lithium iron phosphate: water = 1: 1-10; stirring state Next, adding 0.01-1% of the total weight of the coupling agent, stirring uniformly; adding the above graphene dispersed aqueous solution, stirring, filtering;
3 )、热处理石墨烯和磷酸铁锂材料：过滤得到的固体粉料在真空烘干，在 250-350°C 氮气或氩气气氛下煅烧 2-12小时， 得到被石墨烯包覆的磷酸铁锂正极材料。  3) heat treatment of graphene and lithium iron phosphate material: the solid powder obtained by filtration is vacuum dried and calcined at 250-350 ° C for 2-12 hours under a nitrogen or argon atmosphere to obtain graphene-coated iron phosphate. Lithium cathode material.
2.按照权利要求 1所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法，其特征是: 表面活性剂为苯二胺、 聚乙烯基吡咯烷酮或烷基酚聚氧乙烯醚。  The method for preparing a lithium ion battery composite lithium iron phosphate/carbon according to claim 1, wherein the surfactant is phenylenediamine, polyvinylpyrrolidone or alkylphenol ethoxylate.
3.按照权利要求 1所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法，其特征是: 偶联剂为 Y -巯丙基三甲氧基硅烷、 甲基异丁基酮肟基硅烷或乙烯基三乙氧基硅烷。  The method for preparing a lithium ion battery composite lithium iron phosphate/carbon according to claim 1, wherein the coupling agent is Y-mercaptopropyltrimethoxysilane or methyl isobutyl ketone sulfonylsilane. Or vinyl triethoxysilane.
4. 按照权利要求 1、 2或 3所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法， 其 特征是： 石墨烯分散的水溶液中石墨烯的重量百分比浓度为 1-10%。  The method for preparing a lithium ion battery composite lithium iron phosphate/carbon according to claim 1, 2 or 3, wherein the graphene-dispersed aqueous solution has a graphene concentration of from 1 to 10% by weight.
5.按照权利要求 1、 2或 3所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法， 其 特征是：加入石墨烯分散的水溶液后，在 20-40°C条件下搅拌 4-10小时，然后静置 12-36 小时， 再搅拌。  The method for preparing a lithium ion battery composite lithium iron phosphate/carbon according to claim 1, 2 or 3, characterized in that after adding a graphene dispersed aqueous solution, stirring at 20-40 ° C is carried out 4- 10 hours, then let stand for 12-36 hours, then stir.
6. 按照权利要求 1、 2或 3所述的锂离子电池复合材料磷酸铁锂 /碳的制备方法， 其 特征是： 固体粉料真空烘干时， 真空烘干温度为 120-150°C。  The method for preparing a lithium ion battery composite lithium iron phosphate/carbon according to claim 1, 2 or 3, characterized in that: when the solid powder is vacuum dried, the vacuum drying temperature is 120-150 °C.
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