WO2016201940A1 - Preparation method for carbon/graphite composite anode material - Google Patents

Preparation method for carbon/graphite composite anode material Download PDF

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WO2016201940A1
WO2016201940A1 PCT/CN2015/098495 CN2015098495W WO2016201940A1 WO 2016201940 A1 WO2016201940 A1 WO 2016201940A1 CN 2015098495 W CN2015098495 W CN 2015098495W WO 2016201940 A1 WO2016201940 A1 WO 2016201940A1
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carbon
calcined
graphite
petroleum coke
kneading
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田东
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田东
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 relates to a preparation method of a carbon/graphite composite anode material, and belongs to the technical field of lithium ion batteries.
  • Lithium-ion batteries have rapidly occupied the civilian secondary battery market at an average annual rate of 15%, and have become the first choice for portable electronic devices. power supply.
  • the rapid development of lithium-ion batteries is mainly due to the contribution of electrode materials, especially the improvement of anode materials.
  • Lithium-ion battery anode materials are required to have the following characteristics: 1 as low as possible electrode potential; 2 ions have a higher diffusivity in the negative solid state structure; 3 height deintercalability; 4 good conductivity and thermodynamic stability; 5 good safety performance; 6 good compatibility with electrolyte solvent; 7 rich in resources, low in price, no pollution to the environment.
  • the negative electrode material is one of the four major raw materials (positive electrode, negative electrode, electrolyte, and separator) of the lithium ion battery.
  • the commercial lithium ion battery anode material is made of graphite carbon material, which has a low lithium insertion/deintercalation potential and is suitable. It has the advantages of reversible capacity, abundant resources and low price, and is an ideal anode material for lithium ion batteries.
  • Carbon materials have been widely used in lithium ion batteries because of their low cost, non-toxicity and superior electrochemical properties. Its interface state and fine structure have a great influence on electrode performance.
  • commercial lithium-ion battery carbon anode materials can be divided into graphite, hard carbon and soft carbon. Among them, graphite materials are still the mainstream of lithium-ion battery anode materials.
  • Graphite-based carbon materials which have the advantages of low lithium insertion/deintercalation potential, suitable reversible capacity, abundant resources, and low price, are ideal anode materials for lithium ion batteries. However, its theoretical specific capacity is only 372 mAh/g, which limits the further improvement of the specific energy of lithium-ion batteries and cannot meet the needs of the increasingly high-energy portable mobile power sources.
  • a solid electrolyte membrane (SEI) is formed on the surface during the first charge and discharge process.
  • SEI solid electrolyte membrane
  • the solid electrolyte membrane is formed by reacting an electrolyte, a negative electrode material, and lithium ions, and irreversibly consuming lithium ions, which is a major factor in forming an irreversible capacity.
  • the second is that the electrolyte is easily embedded in the lithium ion intercalation process. During the process of eviction, the electrolyte is reduced, and the resulting gas product causes the graphite sheet to peel off.
  • the graphite sheet peels off and a new interface is formed, resulting in further SEI formation, irreversible capacity increase, and circulation.
  • the stability is degraded.
  • carbon materials still have shortcomings such as low charge and discharge capacity, large irreversible loss of primary circulation, co-insertion of solvent molecules, and high production cost. These are also key issues that need to be addressed in current lithium-ion battery research.
  • Carbon fiber is a new type of carbon material. According to raw materials, there are mainly PAN-based carbon fibers (more than 90% of the carbon fibers on the market), viscose-based carbon fibers, and pitch-based carbon fibers. In general, pitch-based carbon fibers have a lower electrical resistivity than PAN-based carbon fibers, and PAN-based carbon fibers have a lower electrical resistivity than viscose-based carbon fibers.
  • the electron rate decreases as the heat treatment temperature increases.
  • Chinese patent CN 102623704A by adding carbon fiber, using its high conductivity and strong adsorption to prepare lithium carbonate-carbon fiber composite anode material to solve the problem of material large rate charge and discharge performance and improve conductivity, to meet the needs of modern society for lithium ion battery Requirements.
  • Chinese patent CN 102290582A by adding nano-long carbon fiber VGCF, improves battery conductivity and reduces internal resistance.
  • a preparation method of a tin/graphene/carbon fiber composite lithium battery anode material disclosed in Chinese patent CN 104037393A a network structure composed of a mixture of graphene and carbon fiber, provides a large number of smooth transport channels for lithium ion in and out electrodes, so that it can be fully Contact with the anode material improves the utilization efficiency of the anode material. Improve the effective position of lithium storage in the negative electrode material and the transport speed of lithium during charge and discharge.
  • the high electrical conductivity of graphene and carbon fiber can quickly achieve carrier migration, improve output power and effectively reduce the internal resistance of the battery itself.
  • the technical problem to be solved by the present invention is to provide a method for preparing a carbon/graphite composite anode material, which has high-pressure properties, high conductivity and high-rate performance, and long cycle performance.
  • the technical solution adopted by the present invention is:
  • the preparation method of the carbon/graphite composite anode material adopt the following particle size and weight percentage ingredients: carbon black 1.5-2.5%, ⁇ 1mm natural graphite 5-8%, ⁇ 0.075mm calcined petroleum coke powder 25-30%, 1 ⁇ 4mm calcined petroleum coke 15-20%, 4 ⁇ l0mm electric calcined anthracite 10-15%, 10-16mm electric calcined anthracite 5 ⁇ 10%, 10-16mm calcined asphalt coke 5 ⁇ 15%, coal asphalt 18-20%;
  • the chopped carbon fiber is 1 to 3% of the total amount of the above raw materials.
  • the calcined petroleum coke powder and the calcined petroleum coke are calcined at about 1300 °C.
  • the electro-calcined anthracite is calcined by a temperature of about 1100-2000 ° C or higher.
  • the calcined pitch coke is calcined at about 1300 °C.
  • Carbon black is conductive carbon black, acetylene black, semi-reinforcing carbon black and related carbon black, performance indicators and raw
  • the ordinary carbon brush carbon black raw materials are similar.
  • Natural graphite which can be flake graphite or low-ash earthy graphite, has similar performance indexes to natural graphite materials used in the production of ordinary electromechanical carbon graphite products.
  • the coal tar can be medium temperature coal tar pitch or modified coal tar pitch.
  • a preparation method of a carbon/graphite composite anode material the preparation steps thereof include:
  • the carbon/graphite composite material is pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 8 to 25 ⁇ m.
  • the kneading is carried out by first adding carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined pitch coke to a kneading machine, and then adding short after 5-6 minutes.
  • Cut carbon fiber for dry mixing dry mixing time is 35-40 minutes, dry mixing temperature is 120-150 ° C; when the dry mixing temperature reaches the set time and temperature, add 175 ° C -185 ° C coal pitch for wet mixing, The wet mixing time is 30-50 minutes, the kneading temperature is 160-165 ° C, the kneaded paste is cooled, and when the paste temperature is lowered to 125-145 ° C, it is added into the mold to form a composite plastomer.
  • the carbon fiber is a PAN-based chopped carbon fiber or a pitch-based chopped carbon fiber.
  • the chopped carbon fibers may have a length of 10 to 200 mm and an average diameter of 5 to 30 ⁇ m.
  • an organic solvent such as alcohol or acetone is used for dispersion treatment.
  • a lithium-ion battery is a rechargeable battery that relies on lithium ions to move between the positive and negative electrodes to work.
  • Li + is intercalated and deintercalated between the two electrodes: when charging the battery, Li + is deintercalated from the positive electrode, and the negative electrode is in a lithium-rich state through the electrolyte embedded in the negative electrode;
  • the graphite negative electrode material due to good layered structure for embedding a lithium - prolapse interlayer insertion compound of formula LiC x, and has excellent charge and discharge platform, thus being widely used.
  • the SEI film is formed through the interface reaction between the graphite and the electrolyte during the first charge process, resulting in loss of irreversible capacity. Therefore, the theoretical capacity of the graphite negative electrode material is 372 mAh/g. However, in actual use, its capacity is generally 330-360 mAh/g, which is lower than the theoretical capacity.
  • the irreversible capacity loss caused by SEI film production is directly related to the specific surface area of the graphite anode material. The specific surface area of graphite is large, the range of contact between electrolyte and graphite is large, and the generated SEI is too much, resulting in irreversible capacity loss. .
  • the currently widely used graphite coating modification is to coat a modified layer for the specific surface area of graphite to reduce the specific surface area of the material, thereby improving the first discharge efficiency of graphite, increasing its capacity and circulation. Stability performance.
  • the prepared carbon/graphite composite material not only avoids the low crystallinity of the low crystallinity carbon material, the large irreversible capacity loss, and secondly avoids the graphite material in the organic solvent. In the case of co-intercalation, the cycle performance is degraded.
  • the composite material prepared by the invention has the first capacity, high first charge and discharge efficiency, electrolyte solvent resistance, Isotropic and other characteristics. At the same time, the invention has simple production process, excellent product performance and large-scale production.
  • the ingredients are: ⁇ 1mm microcrystalline graphite 5%, ⁇ 0.075mm calcined petroleum coke 28%, 1-4mm calcined petroleum coke 15%, 4 ⁇ l0mm electric calcined anthracite 10%, 10-16mm electric calcined anthracite 5%, 10-16mm Calcined pitch coke 15%, acetylene black 2%, coal pitch 20%.
  • 1% T300PAN chopped carbon fiber (diameter 12 ⁇ m, length 10 mm) with a weight of 1%;
  • (1) compounding and kneading first adding carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined pitch coke to the kneading machine, the dry mixing time is 35 minutes, and the dry mixing temperature is 120 ° C; When the dry mixing temperature reaches the set time and temperature, the coal tar pitch at 175 ° C is added for wet mixing, the wet mixing time is 30 minutes, and the kneading temperature is 160 ° C to form a composite plastomer;
  • the carbon/graphite composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 12.53 ⁇ m.
  • the ingredients are: ⁇ 1mm microcrystalline graphite 5%, ⁇ 0.075mm calcined petroleum coke 28%, 1-4mm calcined petroleum coke 15%, 4 ⁇ l0mm electric calcined anthracite 10%, 10-16mm electric calcined anthracite 5%, 10-16mm Calcined pitch coke 15%, acetylene black 2%, coal pitch 20%. Plus 1% T300PAN chopped carbon fiber (diameter 12 ⁇ m, length 10mm);
  • the carbon/graphite composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 11.63 ⁇ m.
  • Example 2 The formulation of Example 2 was unchanged, and 2% T300PAN chopped carbon fiber (diameter 12 ⁇ m, length 10 mm) was added, and the process was as in Example 1.
  • Example 2 The formulation of Example 2 was unchanged, and 3% T300PAN chopped carbon fiber (diameter 12 ⁇ m, length 10 mm) was added, and the process was as in Example 2.
  • Example 2 The ingredients of Example 2 were used unchanged, and 3% pitch-based chopped carbon fibers (20 ⁇ m in diameter and 10 mm in length) were respectively added, and the process was as in Example 2.
  • the carbon/graphite composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 13.94 ⁇ m.
  • Example 1 First discharge capacity (mAh/g) First charge and discharge efficiency (%) Example 1 350.6 94.5 Example 2 348.9 94.7 Example 3 352.1 95.1 Example 4 349.2 95.3 Example 5 352.3 94.9 Example 6 354.5 95.5
  • the production of the 4244130 soft-packed finished battery was used for the detection of the rate charge and discharge.

Abstract

The present invention relates to a preparation method for a carbon/graphite composite anode material. The raw materials adopt ingredients with grain sizes and percentage by weight as follows: 1.5%-2.5% of carbon black, 5%-8% of natural graphite with the grain size being not greater than 1 mm, 25%-30% of calcined petrol coke powder with the grain size being not greater than 0.075 mm, 15%-20% of calcined petroleum coke with the grain size being 1-4 mm, 10%-15% of electrically calcined anthracite with the grain size being 4-10 mm, 5%-10% of electrically calcined anthracite with the grain size being 10-16 mm, 5%-15% of calcined pitch coke with the grain size being 10-16 mm, 18%-20% of coal pitch, and short carbon fibers, accounting for 1%-3% of the total weight of the aforementioned raw materials. A carbon/graphite composite material is prepared by the following steps: burdening, mixing kneading, roasting, graphitizing, crushing, and balling. In conjunction with respective advantages of carbon materials and graphite materials as anode materials, the composite material prepared in the present invention has the characteristics of high first capacity, high first charge and discharge efficiency, electrolyte solvent resistance, isotropy, and the like.

Description

一种炭/石墨复合负极材料的制备方法Preparation method of carbon/graphite composite anode material 技术领域Technical field
本发明涉及一种炭/石墨复合负极材料的制备方法，属于锂离子电池技术领域。The invention relates to a preparation method of a carbon/graphite composite anode material, and belongs to the technical field of lithium ion batteries.
背景技术Background technique
自上世纪90年代初日本索尼能源技术公司率先成功开发出使用碳负极的锂离子电池以来，锂离子电池以年均15％的速度迅速占领民用二次电池市场，已经成为当前便携式电子设备的首选电源。锂离子电池的飞速发展主要是得益于电极材料的贡献，特别是负极材料的进步。锂离子电池负极材料要求具备以下特点：①尽可能低的电极电位；②离子在负极固态结构中有较高的扩散率；③高度的脱嵌可逆性；④良好的电导率及热力学稳定性；⑤安全性能好；⑥与电解质溶剂相容性好；⑦资源丰富、价格低廉，对环境无污染。负极材料是锂离子电池四大原材料(正极、负极、电解液、隔膜)之一，目前商业化锂离子电池负极材料采用的是石墨类碳材料，具有较低的锂嵌入/脱嵌电位、合适的可逆容量且资源丰富、价格低廉等优点，是比较理想的锂离子电池负极材料。Since the beginning of the 1990s, Japan’s Sony Energy Technology Co., Ltd. has taken the lead in successfully developing lithium-ion batteries using carbon negative electrodes. Lithium-ion batteries have rapidly occupied the civilian secondary battery market at an average annual rate of 15%, and have become the first choice for portable electronic devices. power supply. The rapid development of lithium-ion batteries is mainly due to the contribution of electrode materials, especially the improvement of anode materials. Lithium-ion battery anode materials are required to have the following characteristics: 1 as low as possible electrode potential; 2 ions have a higher diffusivity in the negative solid state structure; 3 height deintercalability; 4 good conductivity and thermodynamic stability; 5 good safety performance; 6 good compatibility with electrolyte solvent; 7 rich in resources, low in price, no pollution to the environment. The negative electrode material is one of the four major raw materials (positive electrode, negative electrode, electrolyte, and separator) of the lithium ion battery. At present, the commercial lithium ion battery anode material is made of graphite carbon material, which has a low lithium insertion/deintercalation potential and is suitable. It has the advantages of reversible capacity, abundant resources and low price, and is an ideal anode material for lithium ion batteries.
碳材料以其价廉、无毒及其优越的电化学性能在锂离子电池中得到了广泛的应用，它本身的界面状况和微细结构对电极性能有很大的影响。目前，商品化的锂离子电池碳负极材料可分为石墨、硬碳和软碳三类，其中石墨类材料依然是锂离子电池负极材料的主流。石墨类碳材料，具有较低的锂嵌入/脱嵌电位、合适的可逆容量且资源丰富、价格低廉等优点，是比较理想的锂离子电池负极材料。但其理论比容量只有372mAh/g，因而限制了锂离子电池比能量的进一步提高，不能满足日益发展的高能量便携式移动电源的需求。同时，石墨作为负极材料时，在首次充放电过程中在其表面形成一层固体电解质膜(SEI)。固体电解质膜是电解液、负极材料和锂离子等相互反应形成，不可逆地消耗锂离子，是形成不可逆容量的一个主要的因素；其二是在锂离子嵌入的过程中，电解质容易与其共嵌在迁出的过程中，电解液被还原，生成的气体产物导致石墨片层剥落，尤其在含有PC的电解液中，石墨片层脱落将形成新界面，导致进一步SEI形成，不可逆容量增加，同时循环稳定性下降。碳材料作为锂离子电池负极材料依然存在充放电容量低、初次循环不可逆损失大、溶剂分子共插层和制备成本高等缺点， 这些也是在目前锂离子电池研究方面所需解决的关键问题。Carbon materials have been widely used in lithium ion batteries because of their low cost, non-toxicity and superior electrochemical properties. Its interface state and fine structure have a great influence on electrode performance. At present, commercial lithium-ion battery carbon anode materials can be divided into graphite, hard carbon and soft carbon. Among them, graphite materials are still the mainstream of lithium-ion battery anode materials. Graphite-based carbon materials, which have the advantages of low lithium insertion/deintercalation potential, suitable reversible capacity, abundant resources, and low price, are ideal anode materials for lithium ion batteries. However, its theoretical specific capacity is only 372 mAh/g, which limits the further improvement of the specific energy of lithium-ion batteries and cannot meet the needs of the increasingly high-energy portable mobile power sources. At the same time, when graphite is used as a negative electrode material, a solid electrolyte membrane (SEI) is formed on the surface during the first charge and discharge process. The solid electrolyte membrane is formed by reacting an electrolyte, a negative electrode material, and lithium ions, and irreversibly consuming lithium ions, which is a major factor in forming an irreversible capacity. The second is that the electrolyte is easily embedded in the lithium ion intercalation process. During the process of eviction, the electrolyte is reduced, and the resulting gas product causes the graphite sheet to peel off. Especially in the electrolyte containing PC, the graphite sheet peels off and a new interface is formed, resulting in further SEI formation, irreversible capacity increase, and circulation. The stability is degraded. As a negative electrode material for lithium ion batteries, carbon materials still have shortcomings such as low charge and discharge capacity, large irreversible loss of primary circulation, co-insertion of solvent molecules, and high production cost. These are also key issues that need to be addressed in current lithium-ion battery research.
碳纤维是一种新型的碳材料，按原材料划分主要有PAN基碳纤维(市场上90％以上为该种碳纤维)、粘胶基碳纤维、沥青基碳纤维等三种。一般来说，沥青基碳纤维的电阻率要比PAN基碳纤维小，PAN基碳纤维电阻率要比粘胶基碳纤维小。电子率都会随着热处理温度的升高而降低。Carbon fiber is a new type of carbon material. According to raw materials, there are mainly PAN-based carbon fibers (more than 90% of the carbon fibers on the market), viscose-based carbon fibers, and pitch-based carbon fibers. In general, pitch-based carbon fibers have a lower electrical resistivity than PAN-based carbon fibers, and PAN-based carbon fibers have a lower electrical resistivity than viscose-based carbon fibers. The electron rate decreases as the heat treatment temperature increases.
中国专利CN 102623704A，通过添加碳纤维，利用其高导电性和强吸附性来制备碳酸锂—碳纤维复合负极材料以解决材料大倍率充放电性能和提高导电性的问题，满足现代社会对锂离子电池应用的要求。中国专利CN 102290582A，通过添加纳米超长碳纤维VGCF，提高电池导电性，降低内阻。Chinese patent CN 102623704A, by adding carbon fiber, using its high conductivity and strong adsorption to prepare lithium carbonate-carbon fiber composite anode material to solve the problem of material large rate charge and discharge performance and improve conductivity, to meet the needs of modern society for lithium ion battery Requirements. Chinese patent CN 102290582A, by adding nano-long carbon fiber VGCF, improves battery conductivity and reduces internal resistance.
中国专利CN 104037393A公布的一种锡/石墨烯/碳纤维复合锂电池负极材料制备方法，石墨烯和碳纤维混合构成的网络结构，为锂离子进出电极提供了大量顺畅的输运通道，使其可充分与负极材料接触，提高负极材料的利用效率。提高负极材料储锂的有效位置及充放电时锂的输运速度。石墨烯和碳纤维的高导电性能可以快速的实现载流子迁移，提高输出功率的同时能够有效地降低电池本身的内阻。A preparation method of a tin/graphene/carbon fiber composite lithium battery anode material disclosed in Chinese patent CN 104037393A, a network structure composed of a mixture of graphene and carbon fiber, provides a large number of smooth transport channels for lithium ion in and out electrodes, so that it can be fully Contact with the anode material improves the utilization efficiency of the anode material. Improve the effective position of lithium storage in the negative electrode material and the transport speed of lithium during charge and discharge. The high electrical conductivity of graphene and carbon fiber can quickly achieve carrier migration, improve output power and effectively reduce the internal resistance of the battery itself.
发明内容Summary of the invention
本发明要解决的技术问题是提供一种炭/石墨复合负极材料的制备方法，该方法制备得到的负极材料具有高压实性能、高导电和高倍率性能，以及长循环性能。The technical problem to be solved by the present invention is to provide a method for preparing a carbon/graphite composite anode material, which has high-pressure properties, high conductivity and high-rate performance, and long cycle performance.
为解决以上技术问题，本发明采用的技术方案是：In order to solve the above technical problems, the technical solution adopted by the present invention is:
一种炭/石墨复合负极材料的制备方法，原料采用如下粒度和重量百分比配料：炭黑1.5-2.5％，≤1mm天然石墨5-8％，≤0.075mm煅烧石油焦粉25-30％，1～4mm煅烧石油焦15-20％，4～l0mm电煅无烟煤10-15％，10-16mm电煅无烟煤5～10％，10-16mm煅烧沥青焦5～15％，煤沥青18-20％；短切碳纤维为以上原料总量的1～3％。The preparation method of the carbon/graphite composite anode material, the raw materials adopt the following particle size and weight percentage ingredients: carbon black 1.5-2.5%, ≤1mm natural graphite 5-8%, ≤0.075mm calcined petroleum coke powder 25-30%, 1 ~ 4mm calcined petroleum coke 15-20%, 4 ~ l0mm electric calcined anthracite 10-15%, 10-16mm electric calcined anthracite 5 ~ 10%, 10-16mm calcined asphalt coke 5 ~ 15%, coal asphalt 18-20%; The chopped carbon fiber is 1 to 3% of the total amount of the above raw materials.
煅烧石油焦粉和煅烧石油焦是经约1300℃煅烧而成。The calcined petroleum coke powder and the calcined petroleum coke are calcined at about 1300 °C.
电煅无烟煤经约1100-2000℃以上温度煅烧而成。The electro-calcined anthracite is calcined by a temperature of about 1100-2000 ° C or higher.
煅烧沥青焦是经约1300℃煅烧而成。The calcined pitch coke is calcined at about 1300 °C.
炭黑为导电炭黑、乙炔炭黑、半补强炭黑以及相关炭黑，性能指标与生 产普通炭刷炭黑原料相近。Carbon black is conductive carbon black, acetylene black, semi-reinforcing carbon black and related carbon black, performance indicators and raw The ordinary carbon brush carbon black raw materials are similar.
天然石墨，可以是鳞片石墨也可以是低灰的土状石墨，性能指标与生产普通机电用炭石墨制品用天然石墨原料相近。Natural graphite, which can be flake graphite or low-ash earthy graphite, has similar performance indexes to natural graphite materials used in the production of ordinary electromechanical carbon graphite products.
煤沥青可以是中温煤沥青亦可以是改质煤沥青。The coal tar can be medium temperature coal tar pitch or modified coal tar pitch.
一种炭/石墨复合负极材料的制备方法，其制备步骤包括：A preparation method of a carbon/graphite composite anode material, the preparation steps thereof include:
(1)配料、混捏，先将炭黑、天然石墨、煅烧石油焦粉、煅烧石油焦、电煅无烟煤和短切碳纤维进行组合配料，经过干混后与煤沥青粘合剂加温捏合，形成复合塑性体；(1) compounding and kneading, firstly combining carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and chopped carbon fiber, after dry mixing, kneading with coal tar pitch binder to form Composite plastomer
(2)焙烧，将复合塑性体直接装入焙烧炉，经过900-1100℃焙烧，制成炭素材料；(2) roasting, directly charging the composite plastomer into a baking furnace, and roasting at 900-1100 ° C to prepare a carbon material;
(3)石墨化，将炭素材料装入石墨化炉，经2200-3000℃高温处理，制得炭/石墨复合材料；(3) Graphitization, the carbon material is charged into a graphitization furnace, and treated at a high temperature of 2200-3000 ° C to obtain a carbon/graphite composite material;
(4)粉碎、球化，将炭/石墨复合材料进行粉碎、球化，得到粒径D50为8～25μm的球形或椭圆形炭/石墨负极粉体。(4) Crushing and spheroidizing, the carbon/graphite composite material is pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 8 to 25 μm.
作为优选的技术方案，所述的混捏，是先将炭黑、天然石墨、煅烧石油焦粉、煅烧石油焦、电煅无烟煤和煅烧沥青焦加入混捏机中，间隔5-6分钟后再加入短切碳纤维进行干混，干混时间为35-40分钟，干混温度为120-150℃；在干混温度达到设定的时间和温度时，加入175℃-185℃的煤沥青进行湿混，湿混时间在30-50分钟，混捏温度为160-165℃，将混捏后的糊料进行凉料，当糊料温度降至125-145℃时，加入模具中形成复合塑性体。As a preferred technical solution, the kneading is carried out by first adding carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined pitch coke to a kneading machine, and then adding short after 5-6 minutes. Cut carbon fiber for dry mixing, dry mixing time is 35-40 minutes, dry mixing temperature is 120-150 ° C; when the dry mixing temperature reaches the set time and temperature, add 175 ° C -185 ° C coal pitch for wet mixing, The wet mixing time is 30-50 minutes, the kneading temperature is 160-165 ° C, the kneaded paste is cooled, and when the paste temperature is lowered to 125-145 ° C, it is added into the mold to form a composite plastomer.
作为优选的技术方案，所述的碳纤维是PAN基短切碳纤维或沥青基短切碳纤维。As a preferred technical solution, the carbon fiber is a PAN-based chopped carbon fiber or a pitch-based chopped carbon fiber.
所述的短切碳纤维长度可以是10-200mm，平均直径是5μm-30μm。在将碳纤维加入混捏机以前先期采用有机溶剂，如酒精、丙酮等进行分散处理。The chopped carbon fibers may have a length of 10 to 200 mm and an average diameter of 5 to 30 μm. Before the carbon fiber is added to the kneader, an organic solvent such as alcohol or acetone is used for dispersion treatment.
锂离子电池是一种充电电池，它主要依靠锂离子在正极和负极之间移动来工作。在充放电过程中，Li+在两个电极之间往返嵌入和脱嵌：充电池时，Li+从正极脱嵌，经过电解质嵌入负极，负极处于富锂状态；放电时则相反。而石墨负极材料由于具有良好的层状结构，适合锂的嵌入—脱出而形成层间***式化合物LiCx，而且具有良好的充放电平台，因此受到广泛应用。而石墨在作为锂离 子电池负极材料，在首次冲电过程中，石墨与电解液界面上通过界面反应会生成SEI膜，造成不可逆容量的损失，因此，石墨负极材料的理论容量为372mAh/g，但在实际使用过程中，其容量发挥一般为330～360mAh/g，低于理论容量。而SEI膜生产所导致的不可逆容量损失与石墨负极材料的比表面积有直接关系，石墨的比表面积大，电解液和石墨接触的范围大，生成的SEI过多，造成的不可逆容量损失也越大。同时，由于石墨尤其在含PC的电解液中，易与电解液发生共嵌，而导致石墨片层剥落，形成新的端面，导致进一步SEI形成，致使循环性能不断降低。因此，目前普遍采用的石墨包覆改性，就是针对石墨的比表面积过大而进行包覆一层改性层来降低材料的比表面积，从而提高石墨的首次放电效率，提升其容量发挥和循环稳定性能。A lithium-ion battery is a rechargeable battery that relies on lithium ions to move between the positive and negative electrodes to work. During charging and discharging, Li + is intercalated and deintercalated between the two electrodes: when charging the battery, Li + is deintercalated from the positive electrode, and the negative electrode is in a lithium-rich state through the electrolyte embedded in the negative electrode; And the graphite negative electrode material due to good layered structure for embedding a lithium - prolapse interlayer insertion compound of formula LiC x, and has excellent charge and discharge platform, thus being widely used. While graphite is used as a negative electrode material for lithium ion batteries, the SEI film is formed through the interface reaction between the graphite and the electrolyte during the first charge process, resulting in loss of irreversible capacity. Therefore, the theoretical capacity of the graphite negative electrode material is 372 mAh/g. However, in actual use, its capacity is generally 330-360 mAh/g, which is lower than the theoretical capacity. The irreversible capacity loss caused by SEI film production is directly related to the specific surface area of the graphite anode material. The specific surface area of graphite is large, the range of contact between electrolyte and graphite is large, and the generated SEI is too much, resulting in irreversible capacity loss. . At the same time, since graphite is especially co-embedded with the electrolyte in the electrolyte containing PC, the graphite sheet peels off and a new end face is formed, resulting in further SEI formation, resulting in a continuous decrease in cycle performance. Therefore, the currently widely used graphite coating modification is to coat a modified layer for the specific surface area of graphite to reduce the specific surface area of the material, thereby improving the first discharge efficiency of graphite, increasing its capacity and circulation. Stability performance.
通过对多种炭材料以及碳材料前驱体的复合处理，所制得的炭/石墨复合材料，不仅避免了低结晶度炭材料容量低、首次不可逆容量损失大，其次避免了石墨材料在有机溶剂中发生共嵌而导致循环性能下降等缺点，通过结合炭材料和石墨类材料作为负极材料时各自的优点，本发明制备的复合材料具有首次容量高、首次充放电效率高、耐电解液溶剂、各向同性等特点。同时本发明生产工艺简单，产品性能优异，能规模化生产。Through the composite treatment of various carbon materials and carbon material precursors, the prepared carbon/graphite composite material not only avoids the low crystallinity of the low crystallinity carbon material, the large irreversible capacity loss, and secondly avoids the graphite material in the organic solvent. In the case of co-intercalation, the cycle performance is degraded. By combining the advantages of the carbon material and the graphite material as the negative electrode material, the composite material prepared by the invention has the first capacity, high first charge and discharge efficiency, electrolyte solvent resistance, Isotropic and other characteristics. At the same time, the invention has simple production process, excellent product performance and large-scale production.
附图说明DRAWINGS
图1.实施例1中材料所制备的电池的循环曲线图。Figure 1. Cyclic graph of the battery prepared from the material of Example 1.
图2.实施例1中材料所制备的电池的倍率放电曲线图。Figure 2. Magnification discharge graph of the battery prepared in the material of Example 1.
具体实施方式detailed description
实施例1Example 1
配料为：≤1mm微晶石墨5％，≤0.075mm煅烧石油焦28％，1～4mm煅烧石油焦15％，4～l0mm电煅无烟煤10％，10-16mm电煅无烟煤5％，10-16mm煅烧沥青焦15％，乙炔炭黑2％，煤沥青20％。外加以上原料重量1％的T300PAN短切碳纤维(直径12μm，长度10mm)；The ingredients are: ≤1mm microcrystalline graphite 5%, ≤0.075mm calcined petroleum coke 28%, 1-4mm calcined petroleum coke 15%, 4~l0mm electric calcined anthracite 10%, 10-16mm electric calcined anthracite 5%, 10-16mm Calcined pitch coke 15%, acetylene black 2%, coal pitch 20%. 1% T300PAN chopped carbon fiber (diameter 12 μm, length 10 mm) with a weight of 1%;
(1)配料、混捏，先将炭黑、天然石墨、煅烧石油焦粉、煅烧石油焦、电煅无烟煤和煅烧沥青焦加入混捏机中，干混时间为35分钟，干混温度为120℃；在干混温度达到设定的时间和温度时，加入175℃的煤沥青进行湿混，湿混时间在30分钟，混捏温度为160℃，形成复合塑性体； (1) compounding and kneading, first adding carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined pitch coke to the kneading machine, the dry mixing time is 35 minutes, and the dry mixing temperature is 120 ° C; When the dry mixing temperature reaches the set time and temperature, the coal tar pitch at 175 ° C is added for wet mixing, the wet mixing time is 30 minutes, and the kneading temperature is 160 ° C to form a composite plastomer;
(2)焙烧，将生坯体装入焙烧炉，经过1100℃焙烧，制成炭素材料；(2) roasting, the green body is charged into a baking furnace, and calcined at 1100 ° C to prepare a carbon material;
(3)石墨化，将炭素材料装入石墨化炉，经2500℃高温处理，制得炭/石墨复合材料；(3) Graphitization, the carbon material is charged into a graphitization furnace, and treated at a high temperature of 2500 ° C to obtain a carbon/graphite composite material;
(4)粉碎、球化，将炭/石墨复合材料进行粉碎、球化，得到粒径D50为12.53μm的球形或椭圆形炭/石墨负极粉体。(4) Crushing and spheroidizing, the carbon/graphite composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 12.53 μm.
实施例2Example 2
配料为：≤1mm微晶石墨5％，≤0.075mm煅烧石油焦28％，1～4mm煅烧石油焦15％，4～l0mm电煅无烟煤10％，10-16mm电煅无烟煤5％，10-16mm煅烧沥青焦15％，乙炔炭黑2％，煤沥青20％。外加1％T300PAN短切碳纤维(直径12μm，长度10mm)；The ingredients are: ≤1mm microcrystalline graphite 5%, ≤0.075mm calcined petroleum coke 28%, 1-4mm calcined petroleum coke 15%, 4~l0mm electric calcined anthracite 10%, 10-16mm electric calcined anthracite 5%, 10-16mm Calcined pitch coke 15%, acetylene black 2%, coal pitch 20%. Plus 1% T300PAN chopped carbon fiber (diameter 12μm, length 10mm);
(1)配料、混捏，先将炭黑、天然石墨、煅烧石油焦粉、煅烧石油焦、电煅无烟煤和煅烧沥青焦加入混捏机中，间隔5-6分钟后再加入短切碳纤维进行干混，干混时间为35分钟，干混温度为120℃；在干混温度达到设定的时间和温度时，加入175℃的煤沥青进行湿混，湿混时间在30分钟，混捏温度为160℃，形成复合塑性体；(1) Ingredients and kneading, first add carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined asphalt coke into the kneading machine, and then add chopped carbon fiber for dry mixing after 5-6 minutes. The dry mixing time is 35 minutes, the dry mixing temperature is 120 ° C; when the dry mixing temperature reaches the set time and temperature, the coal tar pitch at 175 ° C is added for wet mixing, the wet mixing time is 30 minutes, and the kneading temperature is 160 ° C. Forming a composite plastomer;
(2)焙烧，将生坯体装入焙烧炉，经过1100℃焙烧，制成炭素材料；(2) roasting, the green body is charged into a baking furnace, and calcined at 1100 ° C to prepare a carbon material;
(3)石墨化，将炭素材料装入石墨化炉，经2500℃高温处理，制得炭石墨复合材料；(3) Graphitization, the carbon material is charged into a graphitization furnace, and treated at a high temperature of 2500 ° C to obtain a carbon graphite composite material;
(4)粉碎、球化，将炭/石墨复合材料进行粉碎、球化，得到粒径D50为11.63μm的球形或椭圆形炭/石墨负极粉体。(4) Crushing and spheroidizing, the carbon/graphite composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 11.63 μm.
实施例3Example 3
采用实施例2配料不变，外加2％T300PAN短切碳纤维(直径12μm，长度10mm)，工艺如实施例1。The formulation of Example 2 was unchanged, and 2% T300PAN chopped carbon fiber (diameter 12 μm, length 10 mm) was added, and the process was as in Example 1.
实施例4Example 4
采用实施例2配料不变，外加3％T300PAN短切碳纤维(直径12μm，长度10mm)，工艺如实施例2。The formulation of Example 2 was unchanged, and 3% T300PAN chopped carbon fiber (diameter 12 μm, length 10 mm) was added, and the process was as in Example 2.
实施例5Example 5
采用实施例2配料不变，分别外加3％沥青基短切碳纤维(直径20μm，长度10mm)，工艺如实施例2。 The ingredients of Example 2 were used unchanged, and 3% pitch-based chopped carbon fibers (20 μm in diameter and 10 mm in length) were respectively added, and the process was as in Example 2.
实施例6Example 6
配料为：0.1mm微晶石墨8％，0.01mm煅烧石油焦25％，1mm煅烧石油焦20％，4mm电煅无烟煤11％，10mm电煅无烟煤6.5％，10mm煅烧沥青焦10％，乙炔炭黑1.5％，煤沥青18％。外加2％T300PAN短切碳纤维(直径5μm，长度200mm)。将短切碳纤维加入混捏机以前先期采用有机溶剂丙酮进行分散处理；Ingredients: 0.1mm microcrystalline graphite 8%, 0.01mm calcined petroleum coke 25%, 1mm calcined petroleum coke 20%, 4mm electric calcined anthracite 11%, 10mm electric calcined anthracite 6.5%, 10mm calcined asphalt coke 10%, acetylene black 1.5%, coal tar pitch 18%. 2% T300PAN chopped carbon fiber (5 μm in diameter and 200 mm in length) was added. Before the chopped carbon fiber is added to the kneading machine, the organic solvent acetone is used for dispersion treatment;
(1)配料、混捏，先将炭黑、天然石墨、煅烧石油焦粉、煅烧石油焦、电煅无烟煤和煅烧沥青焦加入混捏机中，间隔6分钟后再加入短切碳纤维进行干混，干混时间为40分钟，干混温度为150℃；在干混温度达到设定的时间和温度时，加入185℃的煤沥青进行湿混，湿混时间在50分钟，混捏温度为165℃，将混捏后的糊料进行凉料，当糊料温度降至125℃时，加入模具中形成复合塑性体；(1) Ingredients and kneading, first add carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined asphalt coke into the kneading machine, and then add short-cut carbon fiber for dry mixing after 6 minutes. The mixing time is 40 minutes, the dry mixing temperature is 150 ° C; when the dry mixing temperature reaches the set time and temperature, the 185 ° C coal pitch is added for wet mixing, the wet mixing time is 50 minutes, and the kneading temperature is 165 ° C. The kneaded paste is subjected to a cooling material, and when the temperature of the paste is lowered to 125 ° C, it is added into the mold to form a composite plastomer;
(2)焙烧，将生坯体装入焙烧炉，经过1000℃焙烧，制成炭素材料；(2) roasting, the green body is charged into a baking furnace, and calcined at 1000 ° C to prepare a carbon material;
(3)石墨化，将炭素材料装入石墨化炉，经2500℃高温处理，制得炭石墨复合材料；(3) Graphitization, the carbon material is charged into a graphitization furnace, and treated at a high temperature of 2500 ° C to obtain a carbon graphite composite material;
(4)粉碎、球化，将炭/石墨复合材料进行粉碎、球化，得到粒径D50为13.94μm的球形或椭圆形炭/石墨负极粉体。(4) Crushing and spheroidizing, the carbon/graphite composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 13.94 μm.
电化学性能测试Electrochemical performance test
为检验本发明方法制备的负极材料的性能，用半电池测试方法进行测试，用以上实施例的负极材料：乙炔黑：PVDF(聚偏氟乙烯)＝93：3：4(重量比)，加适量NMP(N-甲基吡咯烷酮)调成浆状，涂布于铜箔上，经真空110℃干燥8小时制成负极片；以金属锂片为对电极，电解液为1mol/L LiPF6/EC+DEC+DMC＝1：1：1，聚丙烯微孔膜为隔膜，组装成电池。充放电电压为0～2.0V，充放电速率为0.2C，对电池性能进行能测试，测试结果见表1。In order to test the performance of the negative electrode material prepared by the method of the present invention, the test was carried out by a half-cell test method using the negative electrode material of the above example: acetylene black: PVDF (polyvinylidene fluoride) = 93:3:4 (weight ratio), plus Appropriate amount of NMP (N-methylpyrrolidone) was slurried, coated on copper foil, dried by vacuum at 110 ° C for 8 hours to prepare a negative electrode sheet; metal lithium sheet was used as a counter electrode, and the electrolyte was 1 mol / L LiPF6 / EC +DEC+DMC=1:1:1, the polypropylene microporous membrane is a membrane and assembled into a battery. The charge and discharge voltage is 0-2.0V, and the charge-discharge rate is 0.2C. The battery performance can be tested. The test results are shown in Table 1.
表1 Table 1
实施例Example 首次放电容量(mAh/g)First discharge capacity (mAh/g) 首次充放电效率(％)First charge and discharge efficiency (%)
实施例1Example 1 350.6350.6 94.594.5
实施例2Example 2 348.9348.9 94.794.7
实施例3Example 3 352.1352.1 95.195.1
实施例4Example 4 349.2349.2 95.395.3
实施例5Example 5 352.3352.3 94.994.9
实施例6Example 6 354.5354.5 95.595.5
为了检测本发明的负极材料在动力电池方面的倍率性能，采用制备成4244130型软包成品电池进行倍率充放电的检测。In order to detect the rate performance of the negative electrode material of the present invention in the power battery, the production of the 4244130 soft-packed finished battery was used for the detection of the rate charge and discharge.
用上实施例的负极材料：SP：SBR(固含量50％)：CMC＝94：2.5：1.5：2(重量比)，加适量去离子水混合均匀调成浆状，涂于铜箔上，在90℃下抽真空干燥；将LiFePO4粉末：SP：KS-6：PVDF＝92：3.5：2：2.5(重量比)，以NMP做溶剂混合均匀进行调浆后，涂于铝箔上，在100℃下抽真空干燥；将干燥后的正、负极极片经过辊压、裁片、卷绕、注液、封口、化成工序，制成磷酸铁锂动力型4244130型软包成品电池(标称容量为2.5Ah)，隔膜为Celgard2400，电解液为1M LiPF6/DMC：EC：DEC，使用动力电池检测装置进行倍率性能的检测，测试结果见表2。Using the negative electrode material of the above example: SP: SBR (solid content 50%): CMC = 94: 2.5: 1.5: 2 (weight ratio), add appropriate amount of deionized water, mix and evenly slurry, apply on copper foil, Vacuum drying at 90 ° C; LiFePO4 powder: SP: KS-6: PVDF = 92: 3.5: 2: 2.5 (weight ratio), mixed with NMP solvent mixture, and then applied to aluminum foil, at 100 Vacuum drying at °C; the dried positive and negative pole pieces are subjected to rolling, cutting, winding, injecting, sealing, and forming processes to produce lithium iron phosphate-powered type 4244130 soft-packed finished battery (nominal capacity) The pressure is 2.5Ah), the diaphragm is Celgard2400, and the electrolyte is 1M LiPF6/DMC:EC:DEC. The power performance test device is used to detect the rate performance. The test results are shown in Table 2.
表2 Table 2
Figure PCTCN2015098495-appb-000001
Figure PCTCN2015098495-appb-000001
以上显示和描述了本发明的基本原理、主要特征及本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明的要求保护范围由所附的权利要求书及其等效物界定。 The basic principles, main features, and advantages of the present invention are shown and described above. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, and that the present invention is only described in the foregoing description and the description of the present invention, without departing from the spirit and scope of the invention. Various changes and modifications are intended to be included within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and their equivalents.

Claims (5)

  1. 一种炭/石墨复合负极材料的制备方法，其特征在于：炭黑1.5-2.5％，≤1mm天然石墨5-8％，≤0.075mm煅烧石油焦粉25-30％，1～4mm煅烧石油焦15-20％，4～l0mm电煅无烟煤10-15％，10-16mm电煅无烟煤5～10％，10-16mm煅烧沥青焦5～15％，煤沥青18-20％；短切碳纤维为以上原料总量的1～3％，步骤包括：(1)配料、混捏，先将炭黑、天然石墨、煅烧石油焦粉、煅烧石油焦、电煅无烟煤和短切碳纤维进行组合配料，经过干混后与煤沥青粘合剂加温捏合，形成复合塑性体；Method for preparing carbon/graphite composite anode material, characterized in that: carbon black 1.5-2.5%, ≤1mm natural graphite 5-8%, ≤0.075mm calcined petroleum coke powder 25-30%, 1-4mm calcined petroleum coke 15-20%, 4~10mm electric calcined anthracite 10-15%, 10-16mm electric calcined anthracite 5-10%, 10-16mm calcined asphalt coke 5-15%, coal pitch 18-20%; chopped carbon fiber is above 1 to 3% of the total amount of raw materials, the steps include: (1) compounding, kneading, first combining carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and chopped carbon fiber, after dry mixing After heating and kneading with the coal tar pitch binder to form a composite plastomer;
    (2)焙烧，将复合塑性体直接装入焙烧炉，经过900-1100℃焙烧，制成炭素材料；(2) roasting, directly charging the composite plastomer into a baking furnace, and roasting at 900-1100 ° C to prepare a carbon material;
    (3)石墨化，将炭素材料装入石墨化炉，经2200-3000℃高温处理，制得炭/石墨复合材料；(3) Graphitization, the carbon material is charged into a graphitization furnace, and treated at a high temperature of 2200-3000 ° C to obtain a carbon/graphite composite material;
    (4)粉碎、球化，将炭/石墨复合材料进行粉碎、球化，得到粒径D50为8～25μm的球形或椭圆形炭/石墨负极粉体。(4) Crushing and spheroidizing, the carbon/graphite composite material is pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite negative electrode powder having a particle diameter D50 of 8 to 25 μm.
  2. 根据权利要求1所述的方法，其特征在于：步骤(1)中所述的混捏，是先将炭黑、天然石墨、煅烧石油焦粉、煅烧石油焦、电煅无烟煤和煅烧沥青焦加入混捏机中，间隔5-6分钟后再加入短切碳纤维进行干混，干混时间为35-40分钟，干混温度为120-150℃；在干混温度达到设定的时间和温度时，加入175℃-185℃的煤沥青进行湿混，湿混时间在30-50分钟，混捏温度为160-165℃，将混捏后的糊料进行凉料，当糊料温度降至125-145℃时，加入模具中形成复合塑性体。The method according to claim 1, wherein the kneading in the step (1) is first adding carbon black, natural graphite, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined pitch coke to the kneading. In the machine, after 5-6 minutes, add chopped carbon fiber for dry mixing, dry mixing time is 35-40 minutes, dry mixing temperature is 120-150 ° C; when the dry mixing temperature reaches the set time and temperature, add The coal tar pitch of 175 ° C -185 ° C is wet mixed, the wet mixing time is 30-50 minutes, the kneading temperature is 160-165 ° C, and the kneaded paste is cooled, when the paste temperature drops to 125-145 ° C , added to the mold to form a composite plastomer.
  3. 根据权利要求1所述的方法，其特征在于：所述的碳纤维是PAN基短切碳纤维或沥青基短切碳纤维。The method of claim 1 wherein said carbon fibers are PAN-based chopped carbon fibers or pitch-based chopped carbon fibers.
  4. 根据权利要求1或6所述的方法，其特征在于：所述的短切碳纤维长度可以是10-200mm，平均直径是5μm-30μm。The method according to claim 1 or 6, wherein said chopped carbon fibers have a length of from 10 to 200 mm and an average diameter of from 5 μm to 30 μm.
  5. 根据权利要求1或2所述的方法，其特征在于：在将短切碳纤维加入混捏机以前先期采用有机溶剂进行分散处理。 The method according to claim 1 or 2, characterized in that the organic solvent is used for the dispersion treatment before the chopped carbon fibers are fed to the kneader.
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