WO2016202164A1 - Preparation method for preparing composite carbon/graphite/tin negative-electrode material - Google Patents

Preparation method for preparing composite carbon/graphite/tin negative-electrode material Download PDF

Info

Publication number
WO2016202164A1
WO2016202164A1 PCT/CN2016/083774 CN2016083774W WO2016202164A1 WO 2016202164 A1 WO2016202164 A1 WO 2016202164A1 CN 2016083774 W CN2016083774 W CN 2016083774W WO 2016202164 A1 WO2016202164 A1 WO 2016202164A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
graphite
calcined
tin
petroleum coke
Prior art date
Application number
PCT/CN2016/083774
Other languages
French (fr)
Chinese (zh)
Inventor
田东
Original Assignee
田东
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 田东 filed Critical 田东
Publication of WO2016202164A1 publication Critical patent/WO2016202164A1/en

Links

Classifications

    • 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
    • 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
    • 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 relates to a preparation method of a carbon/graphite/tin 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. But its theory The 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 supply.
  • 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.
  • 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.
  • Metal tin has the advantages of high lithium storage capacity (994 mAh/g) and low lithium ion deintercalation platform voltage, and is a non-carbon negative electrode material with great development potential. In recent years, extensive research has been carried out on such materials and some progress has been made. However, in the process of reversible lithium storage, the volume expansion of metallic tin is remarkable, resulting in poor cycle performance and rapid decay of capacity, so it is difficult to meet the requirements of large-scale production. For this reason, by introducing a non-metallic element such as carbon, the metal tin is stabilized by alloying or compounding, and the volume expansion of tin is slowed down. Carbon can prevent direct contact between tin particles, inhibit the agglomeration and growth of tin particles, and act as a buffer layer.
  • the heat resistance of the tin-carbon composite material can be improved by introducing a substance having a high melting point.
  • nickel is a metal with good electrical conductivity
  • melting point is 1453 ° C
  • introduced into the tin carbon composite material can improve the heat treatment temperature of the composite material and obtain good Good electrode material for electrochemical performance.
  • Renzong Hu et al. prepared a core-shell and multi-scale Sn-C-Ni anode material by electron beam evaporation, which exhibited excellent capacity retention and high rate performance.
  • He Chunnian et al. prepared a two-dimensional porous graphitized carbon-coated nickel-tin alloy material by pyrolysis, which has high specific capacity and excellent cycle performance for lithium ion battery anodes (application number 201310715142.1).
  • the technical problem to be solved by the present invention is to provide a method for preparing a carbon/graphite/tin composite anode material, and the anode material prepared by the method has high-pressure solid performance, high conductivity and high rate performance, and long cycle performance.
  • the technical solution adopted by the present invention is:
  • a preparation method of carbon/graphite/tin composite anode material adopt the following particle size and weight percentage ingredients: carbon black 1.5-2.5%, ⁇ 1mm natural graphite 5-8%, ⁇ 100nm nano tin 3-10%, ⁇ 0.075 Mm 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 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, and the performance index is similar to that of ordinary carbon brush carbon black.
  • 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/tin composite anode material the preparation steps thereof include:
  • the carbon/graphite/tin composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite/tin negative electrode powder having a particle diameter D50 of 8 to 25 ⁇ m.
  • the kneading is first introduced into the kneader by carbon black, natural graphite, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined pitch coke, after 5-6 minutes.
  • dry mixing time 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 tar pitch
  • wet mixing time is 30-50 minutes, kneading temperature is 160-165 ° C, the kneaded paste is cooled, and when the paste temperature drops 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 anode material is widely used because it has a good layered structure and is suitable for lithium intercalation to form an interlayer intercalation compound LiC x and has a good charge and discharge platform.
  • 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 carbon/graphite/tin composite material not only avoids the low crystallinity of the low crystallinity carbon material, but also avoids the large irreversible capacity loss, and secondly avoids
  • the co-intercalation of graphite materials in organic solvents leads to defects such as decreased cycle performance.
  • the composite materials can effectively alleviate the volume effect of tin during charging, and the advantages of combining carbon materials and graphite materials and tin powder as negative electrode materials.
  • the composite material prepared by the invention has the first capacity and the first charge and discharge High efficiency, resistance to electrolyte solvents, isotropy and so on. At the same time, the invention has simple production process, excellent product performance and large-scale production.
  • the ingredients are: ⁇ 1mm microcrystalline graphite 5%, ⁇ 100nm nano tin 5%, ⁇ 0.075mm calcined petroleum coke 26%, 1-4mm calcined petroleum coke 15%, 4 ⁇ 10mm electric calcined anthracite 10%, 10-16mm electric calcination Anthracite 5%, 10-16mm calcined asphalt coke 14%, acetylene black 2%, coal asphalt 18%.
  • T300PAN chopped carbon fiber (diameter 12 ⁇ m, length 10 mm) with a weight of 1% of the raw material was added, and the preparation steps were as follows:
  • Ingredients and kneading first add carbon black, natural graphite, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined asphalt 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, adding 175 ° C coal pitch for wet mixing, wet mixing time of 30 minutes, kneading temperature of 160 ° C, forming a composite plastomer;
  • the carbon/graphite/tin composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite/tin negative electrode powder having a particle diameter D50 of 12.53 ⁇ m.
  • the ingredients are: ⁇ 1mm microcrystalline graphite 5%, ⁇ 100nm nano tin 10%, ⁇ 0.075mm calcined petroleum coke 25%, 1-4mm calcined petroleum coke 13%, 4 ⁇ 10mm electric calcined anthracite 8%, 10-16mm electric calcination Anthracite 5%, 10-16mm calcined asphalt coke 14%, acetylene black 2%, Coal tar pitch 18%.
  • Add 1% T300PAN chopped carbon fiber (diameter 12 ⁇ m, length 10mm) the preparation steps are as follows:
  • 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/tin composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite/tin negative electrode powder having a particle diameter D50 of 13.94 ⁇ m.
  • Example 1 Example First discharge capacity (mAh/g) First charge and discharge efficiency (%) Example 1 390.6 94.5 Example 2 448.9 93.7 Example 3 452.1 93.1 Example 4 449.2 93.3 Example 5 452.3 93.9 Example 6 394.5 94.7
  • Example 1 2966.90 88.91 Example 2 3050.13 87.84
  • Example 3 3060.37 87.14
  • Example 4 3055.59 86.03
  • Example 5 3061.32 85.45
  • Example 6 2970.14 88.73

Abstract

The present invention relates to a method for preparing a composite carbon/graphite/tin negative-electrode material. The following raw materials in percentage by weight and particle size are used: 1.5-2.5% of carbon black, 5-8% of natural graphite with a particle size of smaller than or equal to 1 mm, 3-10% of nanosized tin with a particle size of smaller than or equal to 100 nm, 25-30% of calcined petroleum coke powder with a particle size of smaller than or equal to 0.075 mm, 15-20% of calcined petroleum coke with a particle size of 1-4 mm, 10-15% of electrically calcined anthracite with a particle size of 4-10 mm, 5-10% of electrically calcined anthracite with a particle size of 10-16 mm, 5-15% of calcined pitch coke with a particle size of 10-16 mm, 18-20% of coal pitch, and short carbon fibers, the short carbon fibers accounting for 1-3% of the total amount of the raw materials. The composite carbon/graphite/tin material is prepared by burdening, mixing and kneading, roasting, graphitization, crushing, and spheroidization. Integrating the respective advantages of carbon materials, graphite materials, and tin powder as negative-electrode materials, the composite material prepared according to the present invention has such advantages as high initial capacity, high initial charge and discharge efficiency, resistance to electrolyte solvents, and isotropy.

Description

一种炭/石墨/锡复合负极材料的制备方法Preparation method of carbon/graphite/tin composite anode material 技术领域Technical field
本发明涉及一种炭/石墨/锡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/tin 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. But its theory The 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 supply. 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 the key problems to be solved in the research of lithium ion batteries.
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一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.
金属锡具有高的储锂容量(994mAh/g)和低的锂离子脱嵌平台电压等优点，是一种极具发展潜力的非碳负极材料。近年来人们对这类材料开展了广泛的研究，并取得了一定的进展。但在可逆储锂过程中，金属锡体积膨胀显著，导致循环性能变差，容量迅速衰减，因此难以满足大规模生产的要求。为此，通过引入碳等非金属元素，以合金化或复合的方式来稳定金属锡，减缓锡的体积膨胀。碳能够阻止锡颗粒间的直接接触，抑制锡颗粒的团聚和长大，起到缓冲层的作用。Metal tin has the advantages of high lithium storage capacity (994 mAh/g) and low lithium ion deintercalation platform voltage, and is a non-carbon negative electrode material with great development potential. In recent years, extensive research has been carried out on such materials and some progress has been made. However, in the process of reversible lithium storage, the volume expansion of metallic tin is remarkable, resulting in poor cycle performance and rapid decay of capacity, so it is difficult to meet the requirements of large-scale production. For this reason, by introducing a non-metallic element such as carbon, the metal tin is stabilized by alloying or compounding, and the volume expansion of tin is slowed down. Carbon can prevent direct contact between tin particles, inhibit the agglomeration and growth of tin particles, and act as a buffer layer.
虽然锡碳材料的研究获得了较大的进步，但是金属锡的熔点只有232℃，其在进行高温热处理时不可避免地发生体积膨胀。当前，对锡碳材料进行热处理时，主要面临着以下一些问题。锡碳复合材料在较高温热处理时，锡颗粒较容易融合在一起团聚成大颗粒，在循环过程中电极材料粉化脱落，导致电池容量的迅速降低和循环性能变差；在低温热处理时，锡碳复合材料的电阻大，导电性不好。因此，为了提高锡碳复合材料的导电性以及缓解金属锡颗粒在较高热处理温度下团聚现象，可以通过引入具有高熔点的物质来提高锡碳复合材料的耐热性。其中，镍是具有良好导电性的金属，熔点为1453℃，引入到锡碳复合材料中能够提高复合材料热处理温度并获得具有良 好电化学性能的负极材料。Renzong Hu等采用电子束蒸镀法制备了具有核壳以及多尺度的Sn-C-Ni负极材料，该电极材料表现出优异的容量保持率以及高的倍率性能。何春年等采用热解法制备了二维多孔石墨化碳包覆镍锡合金材料，其用于锂离子电池负极具有很高的比容量与极好的循环性能(申请号201310715142.1)。Although the research on tin carbon materials has made great progress, the melting point of metal tin is only 232 ° C, which inevitably causes volume expansion during high temperature heat treatment. At present, when heat treatment of tin carbon materials, the following problems are mainly faced. When the tin-carbon composite material is heat treated at a higher temperature, the tin particles are more easily fused together to form a large particle, and the electrode material is pulverized and detached during the cycle, resulting in rapid decrease in battery capacity and deterioration in cycle performance; in low-temperature heat treatment, tin Carbon composites have large electrical resistance and poor electrical conductivity. Therefore, in order to improve the conductivity of the tin-carbon composite material and to alleviate the agglomeration phenomenon of the metal tin particles at a higher heat treatment temperature, the heat resistance of the tin-carbon composite material can be improved by introducing a substance having a high melting point. Among them, nickel is a metal with good electrical conductivity, melting point is 1453 ° C, introduced into the tin carbon composite material can improve the heat treatment temperature of the composite material and obtain good Good electrode material for electrochemical performance. Renzong Hu et al. prepared a core-shell and multi-scale Sn-C-Ni anode material by electron beam evaporation, which exhibited excellent capacity retention and high rate performance. He Chunnian et al. prepared a two-dimensional porous graphitized carbon-coated nickel-tin alloy material by pyrolysis, which has high specific capacity and excellent cycle performance for lithium ion battery anodes (application number 201310715142.1).
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/锡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/tin composite anode material, and the anode material prepared by the method has high-pressure solid performance, 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/锡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％，≤100nm纳米锡3-10％，≤0.075mm煅烧石油焦粉25-30％，1～4mm煅烧石油焦15-20％，4～10mm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％。A preparation method of carbon/graphite/tin 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%, ≤100nm nano tin 3-10%, ≤0.075 Mm 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 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, and the performance index is similar to that of ordinary carbon brush carbon black.
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/锡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/tin composite anode material, the preparation steps thereof include:
(1)配料、混捏，先将炭黑、天然石墨、纳米锡、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) Ingredients, kneading, first combine carbon black, natural graphite, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and chopped carbon fiber, after dry mixing and heating with coal asphalt binder Kneading 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/锡复合材料；(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/tin composite material;
(4)粉碎、球化，将炭/石墨/锡复合材料进行粉碎、球化，得到粒径D50为8～25μm的球形或椭圆形炭/石墨/锡负极粉体。(4) Crushing and spheroidizing, the carbon/graphite/tin composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite/tin 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、纳米锡、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 first introduced into the kneader by carbon black, natural graphite, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined pitch coke, after 5-6 minutes. Then 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 175 ° C -185 ° C coal tar pitch Wet mixing, wet mixing time is 30-50 minutes, kneading temperature is 160-165 ° C, the kneaded paste is cooled, and when the paste temperature drops 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，适合锂的嵌入一脱出而形成层间***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; The graphite anode material is widely used because it has a good layered structure and is suitable for lithium intercalation to form an interlayer intercalation compound LiC x and has a good charge and discharge platform. 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以及纳米锡的复合处理，所制得的炭/石墨/锡复合材料，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，同时复合材料能有效缓解锡在充电过程中的体积效应，通过结合炭材料和石墨类材料以及锡粉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 combination of various carbon materials and carbon material precursors and nano tin, the carbon/graphite/tin composite material not only avoids the low crystallinity of the low crystallinity carbon material, but also avoids the large irreversible capacity loss, and secondly avoids The co-intercalation of graphite materials in organic solvents leads to defects such as decreased cycle performance. At the same time, the composite materials can effectively alleviate the volume effect of tin during charging, and the advantages of combining carbon materials and graphite materials and tin powder as negative electrode materials. The composite material prepared by the invention has the first capacity and the first charge and discharge High efficiency, resistance to electrolyte solvents, isotropy and so on. At the same time, the invention has simple production process, excellent product performance and large-scale production.
具体实施方式detailed description
实施例1Example 1
配料为：≤1mm微晶石墨5％，≤100nm纳米锡5％，≤0.075mm煅烧石油焦26％，1～4mm煅烧石油焦15％，4～10mm电煅无烟煤10％，10-16mm电煅无烟煤5％，10-16mm煅烧沥青焦14％，乙炔炭黑2％，煤沥青18％。外加以上原料重量1％的T300PAN短切碳纤维(直径12μm，长度10mm)，制备步骤如下：The ingredients are: ≤1mm microcrystalline graphite 5%, ≤100nm nano tin 5%, ≤0.075mm calcined petroleum coke 26%, 1-4mm calcined petroleum coke 15%, 4~10mm electric calcined anthracite 10%, 10-16mm electric calcination Anthracite 5%, 10-16mm calcined asphalt coke 14%, acetylene black 2%, coal asphalt 18%. T300PAN chopped carbon fiber (diameter 12 μm, length 10 mm) with a weight of 1% of the raw material was added, and the preparation steps were as follows:
(1)配料、混捏，先将炭黑、天然石墨、纳米锡、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) Ingredients and kneading, first add carbon black, natural graphite, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined asphalt 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, adding 175 ° C coal pitch for wet mixing, wet mixing time of 30 minutes, kneading temperature of 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/锡复合材料；(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/tin composite material;
(4)粉碎、球化，将炭/石墨/锡复合材料进行粉碎、球化，得到粒径D50为12.53μm的球形或椭圆形炭/石墨/锡负极粉体。(4) Crushing and spheroidizing, the carbon/graphite/tin composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite/tin 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％，≤100nm纳米锡10％，≤0.075mm煅烧石油焦25％，1～4mm煅烧石油焦13％，4～10mm电煅无烟煤8％，10-16mm电煅无烟煤5％，10-16mm煅烧沥青焦14％，乙炔炭黑2％， 煤沥青18％。外加1％T300PAN短切碳纤维(直径12μm，长度10mm)，制备步骤如下：The ingredients are: ≤1mm microcrystalline graphite 5%, ≤100nm nano tin 10%, ≤0.075mm calcined petroleum coke 25%, 1-4mm calcined petroleum coke 13%, 4~10mm electric calcined anthracite 8%, 10-16mm electric calcination Anthracite 5%, 10-16mm calcined asphalt coke 14%, acetylene black 2%, Coal tar pitch 18%. Add 1% T300PAN chopped carbon fiber (diameter 12μm, length 10mm), the preparation steps are as follows:
(1)配料、混捏，先将炭黑、天然石墨、纳米锡、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, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined asphalt coke to the kneading machine, and then add chopped carbon fiber after 5-6 minutes. Dry mixing, dry mixing time is 35 minutes, dry mixing temperature is 120 ° C; when the dry mixing temperature reaches the set time and temperature, add 175 ° C coal pitch for wet mixing, wet mixing time is 30 minutes, kneading temperature Forming a composite plastomer at 160 ° C;
(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/锡复合材料进行粉碎、球化，得到粒径D50为11.63μm的球形或椭圆形炭/石墨/锡负极粉体。(4) Pulverization and spheroidization, the carbon/graphite/tin composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite/tin 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6 Example 6
配料为：0.1mm微晶石墨8％，≤100nm纳米锡7％，0.01mm煅烧石油焦25％，1mm煅烧石油焦15％，4mm电煅无烟煤10％，10mm电煅无烟煤5.5％，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，制备步骤如下：Ingredients: 0.1mm microcrystalline graphite 8%, ≤100nm nano tin 7%, 0.01mm calcined petroleum coke 25%, 1mm calcined petroleum coke 15%, 4mm electric calcined anthracite 10%, 10mm electric calcined anthracite 5.5%, 10mm calcined asphalt 10% coke, 1.5% acetylene black, 18% coal tar. 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 kneader, the organic solvent acetone is used for dispersion treatment. The preparation steps are as follows:
(1)配料、混捏，先将炭黑、天然石墨、纳米锡、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, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined asphalt coke to the kneading machine, and then add chopped carbon fiber to dry after 6 minutes. Mixing, dry mixing time is 40 minutes, dry mixing temperature is 150 ° C; when the dry mixing temperature reaches the set time and temperature, 185 ° C coal pitch is added for wet mixing, wet mixing time is 50 minutes, mixing temperature is 165 °C, the kneaded paste is cooled, when the temperature of the paste drops 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/锡复合材料进行粉碎、球化，得到粒径D50为13.94μm的球形或椭圆形炭/石墨/锡负极粉体。(4) Crushing and spheroidizing, the carbon/graphite/tin composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite/tin 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 properties 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, polypropylene microporous membrane As a diaphragm, 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1Table 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 1 390.6390.6 94.594.5
实施例2Example 2 448.9448.9 93.793.7
实施例3Example 3 452.1452.1 93.193.1
实施例4Example 4 449.2449.2 93.393.3
实施例5Example 5 452.3452.3 93.993.9
实施例6Example 6 394.5394.5 94.794.7
为了检测本发明的负极材料在电池方面的循环性能，采用制备成4244130型软包成品电池进行充放电的检测。In order to test the cycle performance of the negative electrode material of the present invention in terms of battery, a 4244130 type soft-packed finished battery was used for charge and discharge detection.
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，使用电池检测装置进行循环性能的检测，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), adding an appropriate amount of deionized water, mixing and evenly slurrying, coating 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 was 2.5 Ah), the separator was Celgard 2400, and the electrolyte was 1 M LiPF6/DMC:EC:DEC. The cycle performance was tested using a battery tester. The test results are shown in Table 2.
表2 Table 2
实施例Example 1C放电1C discharge 1C充放电1000次容量保持率(％)1C charge and discharge 1000 times capacity retention rate (%)
实施例1Example 1 2966.902966.90 88.9188.91
实施例2Example 2 3050.133050.13 87.8487.84
实施例3Example 3 3060.373060.37 87.1487.14
实施例4Example 4 3055.593055.59 86.0386.03
实施例5Example 5 3061.323061.32 85.4585.45
实施例6Example 6 2970.142970.14 88.7388.73
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/锡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％，≤100nm纳米锡3-10％，≤0.075mm煅烧石油焦粉25-30％，1～4mm煅烧石油焦15-20％，4～10mm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：Method for preparing carbon/graphite/tin composite anode material, characterized in that: carbon black 1.5-2.5%, ≤1mm natural graphite 5-8%, ≤100nm nano tin 3-10%, ≤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 Asphalt 18-20%; chopped carbon fiber is 1 to 3% of the total amount of the above raw materials, and the steps include:
    (1)配料、混捏，先将炭黑、天然石墨、纳米锡、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) Ingredients, kneading, first combine carbon black, natural graphite, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and chopped carbon fiber, after dry mixing and heating with coal asphalt binder Kneading 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/锡复合材料；(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/tin composite material;
    (4)粉碎、球化，将炭/石墨/锡复合材料进行粉碎、球化，得到粒径D50为8～25μm的球形或椭圆形炭/石墨/锡负极粉体。(4) Crushing and spheroidizing, the carbon/graphite/tin composite material was pulverized and spheroidized to obtain a spherical or elliptical carbon/graphite/tin 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、纳米锡、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, characterized in that the kneading in the step (1) is firstly carbon black, natural graphite, nano tin, calcined petroleum coke powder, calcined petroleum coke, electric calcined anthracite and calcined asphalt. The coke is added to the kneading machine, and after 5-6 minutes, the chopped carbon fiber is added for dry mixing. The dry mixing time is 35-40 minutes, the dry mixing temperature is 120-150 ° C; the dry mixing temperature reaches the set time and temperature. When adding 787 ° C -185 ° C coal pitch for wet mixing, wet mixing time is 30-50 minutes, mixing temperature is 160-165 ° C, after mixing The paste is subjected to a cooling material, and when the temperature of the paste is lowered to 125-145 ° C, it is 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.
PCT/CN2016/083774 2015-06-17 2016-05-28 Preparation method for preparing composite carbon/graphite/tin negative-electrode material WO2016202164A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510336209.XA CN104953100A (en) 2015-06-17 2015-06-17 Preparation method of carbon/graphite/tin composite anode material
CN201510336209.X 2015-06-17

Publications (1)

Publication Number Publication Date
WO2016202164A1 true WO2016202164A1 (en) 2016-12-22

Family

ID=54167608

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/083774 WO2016202164A1 (en) 2015-06-17 2016-05-28 Preparation method for preparing composite carbon/graphite/tin negative-electrode material

Country Status (2)

Country Link
CN (1) CN104953100A (en)
WO (1) WO2016202164A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745129A (en) * 2019-10-30 2021-05-04 吉林炭素有限公司 Manufacturing method of carbon ceramic slag stopping back plate
CN116282014A (en) * 2023-03-13 2023-06-23 中国矿业大学 Preparation method and application of coal-based porous carbon material
CN117263706A (en) * 2023-10-07 2023-12-22 湖北东南佳新材料有限公司 Wear-resistant low-resistance carbon material and preparation method thereof

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104953100A (en) * 2015-06-17 2015-09-30 田东 Preparation method of carbon/graphite/tin composite anode material
CN107551940B (en) * 2017-10-23 2023-09-01 北京华索科技股份有限公司 Method and system for intelligently filling asphalt into kneading pot for carbon forming
CN108630926B (en) * 2018-05-07 2021-09-03 中国科学院成都有机化学有限公司 Lithium-sulfur battery positive electrode containing short carbon fiber filaments and preparation method thereof
CN109728289A (en) * 2019-01-11 2019-05-07 暨南大学 A kind of preparation method of lithium electronics composite negative pole material
CN111215633A (en) * 2020-01-14 2020-06-02 大同新成新材料股份有限公司 Method for preparing lithium ion negative electrode material by using tin graphene composite material
CN113501515A (en) * 2021-07-29 2021-10-15 濮方正 Innovative process for manufacturing anthracite into conductor material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1913200A (en) * 2006-08-22 2007-02-14 深圳市贝特瑞电子材料有限公司 Silicon carbone compound negative polar material of lithium ion battery and its preparation method
CN102800852A (en) * 2012-08-28 2012-11-28 湖南德天新能源科技有限公司 Preparation method of negative electrode material of power lithium-ion battery
CN103531758A (en) * 2013-09-11 2014-01-22 安泰科技股份有限公司 Nano metal tin and graphite composite negative electrode material and preparation method thereof
CN104953100A (en) * 2015-06-17 2015-09-30 田东 Preparation method of carbon/graphite/tin composite anode material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103956496A (en) * 2014-04-29 2014-07-30 长沙格翎电池材料有限公司 Lithium ion battery negative active material and preparation method thereof
CN104649263B (en) * 2015-03-06 2016-08-24 山西亮宇炭素有限公司 The preparation method of carbon graphite composite material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1913200A (en) * 2006-08-22 2007-02-14 深圳市贝特瑞电子材料有限公司 Silicon carbone compound negative polar material of lithium ion battery and its preparation method
CN102800852A (en) * 2012-08-28 2012-11-28 湖南德天新能源科技有限公司 Preparation method of negative electrode material of power lithium-ion battery
CN103531758A (en) * 2013-09-11 2014-01-22 安泰科技股份有限公司 Nano metal tin and graphite composite negative electrode material and preparation method thereof
CN104953100A (en) * 2015-06-17 2015-09-30 田东 Preparation method of carbon/graphite/tin composite anode material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745129A (en) * 2019-10-30 2021-05-04 吉林炭素有限公司 Manufacturing method of carbon ceramic slag stopping back plate
CN112745129B (en) * 2019-10-30 2023-04-07 吉林炭素有限公司 Manufacturing method of carbon ceramic slag stopping back plate
CN116282014A (en) * 2023-03-13 2023-06-23 中国矿业大学 Preparation method and application of coal-based porous carbon material
CN117263706A (en) * 2023-10-07 2023-12-22 湖北东南佳新材料有限公司 Wear-resistant low-resistance carbon material and preparation method thereof

Also Published As

Publication number Publication date
CN104953100A (en) 2015-09-30

Similar Documents

Publication Publication Date Title
WO2016201940A1 (en) Preparation method for carbon/graphite composite anode material
WO2016202164A1 (en) Preparation method for preparing composite carbon/graphite/tin negative-electrode material
WO2016169149A1 (en) Recycling method for graphite fine powder to act as lithium ion battery negative electrode material
WO2016074479A1 (en) Pyrolytic amorphous carbon material, preparation method and use thereof
CN107706387B (en) Composite negative electrode material, preparation method thereof and lithium ion battery
CN112670461B (en) Natural graphite carbon coated negative electrode material, preparation method thereof and lithium ion battery
WO2017008606A1 (en) Method for fabricating graphite tin-based composite negative-electrode material
CN114447305B (en) Multi-carbon-based quick-charge anode composite material and preparation method thereof
WO2017206299A1 (en) Method for preparing modified graphite cathode material for lithium-ion batteries
CN113659125B (en) Silicon-carbon composite material and preparation method thereof
WO2017024897A1 (en) Preparation method for modified lithium-ion battery negative electrode material
CN105826561A (en) Method for preparing high-magnification lithium ion battery cathode material
CN113206249B (en) Lithium battery silicon-oxygen composite anode material with good electrochemical performance and preparation method thereof
WO2016201982A1 (en) Graphite anode slurry of lithium ion battery and preparation method therefor
WO2023083147A1 (en) Negative electrode active material, negative electrode plate comprising negative electrode active material, and lithium ion battery
US20210408542A1 (en) Negative electrode material for lithium ion battery, negative electrode for lithium ion battery, lithium ion battery, battery pack and battery powered vehicle
WO2016192542A1 (en) Method for manufacturing modified graphite negative electrode material
CN115714170B (en) Preparation method of high-energy-density quick-charge anode material
CN104600246A (en) Lithium ion battery electrode based on graphene and preparation method thereof
CN114597326A (en) Negative electrode active material, negative plate containing negative electrode active material and battery
CN104882590A (en) Preparation method of carbon/ graphite/ silicon composited anode material
CN102255071A (en) Modified graphite material as well as manufacturing method and application thereof
CN110970599B (en) Graphene-based composite negative electrode material, preparation method thereof and lithium ion battery
CN116230895A (en) Lithium battery cathode material, lithium battery and preparation method
CN110429272A (en) The silicon-carbon composite cathode material and preparation method thereof of one type dragon fruit structure

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16810905

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16810905

Country of ref document: EP

Kind code of ref document: A1