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WO2016169149A1 - 一种石墨细粉作为锂离子电池负极材料的循环利用方法 - Google Patents

一种石墨细粉作为锂离子电池负极材料的循环利用方法 Download PDF

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WO2016169149A1
WO2016169149A1 PCT/CN2015/085813 CN2015085813W WO2016169149A1 WO 2016169149 A1 WO2016169149 A1 WO 2016169149A1 CN 2015085813 W CN2015085813 W CN 2015085813W WO 2016169149 A1 WO2016169149 A1 WO 2016169149A1
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graphite
powder
negative electrode
electrode material
resin
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PCT/CN2015/085813
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English (en)
French (fr)
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鲍海友
田东
张贵萍
谌江宏
鲍丹
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深圳市斯诺实业发展有限公司
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Publication of WO2016169149A1 publication Critical patent/WO2016169149A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of energy and relates to a method for a negative electrode material, in particular to an ultrafine graphite powder--"tail material" produced in the production process of a graphite anode material as a raw material, which is recycled by treatment and used as lithium.
  • a method of ion battery anode material is also considered.
  • Power battery refers to the battery used in electric vehicles, including lithium ion batteries, lead acid batteries, fuel cells, etc.
  • lithium ion batteries have higher specific energy, higher specific power, less self-discharge, long service life and good safety.
  • Other advantages have become the focus of current development in various countries.
  • the graphite material as the anode material of the lithium ion battery has the advantages of low lithium insertion/deintercalation potential, suitable reversible capacity, abundant resources, and low price, and is an ideal anode material for lithium ion batteries.
  • graphite is not only widely used in general industrial and consumer fields, but also widely used in some special industrial fields.
  • the low-end and disorderly development caused by the increasingly expanding market demand has adversely affected China's resource protection and industrial upgrading.
  • graphite is required to be pulverized by a pulverizer for a plurality of times, and then spheroidized by a spheroidizing machine.
  • the use of such a process has the disadvantages of low utilization rate of raw materials and poor environment. Since each pulverization and spheroidization needs to be collected after grading, the intermediate semi-finished products are processed for the next time, and each grading will reduce the utilization rate of raw materials.
  • the final yield of such a negative electrode material production method is 40% to 50%.
  • the remaining 50% to 60% becomes a “tailing material”.
  • the graphite fine powder “tailing material” has small particle size, high specific surface area and low tap density, and can no longer be used as a negative electrode material for lithium ion batteries.
  • various conventional modification methods for graphite are mainly based on surface carbon coating.
  • a layer of pyrolytic carbon on the surface of the graphite, the effect of the organic solvent and the graphite body can be effectively prevented, thereby preventing lithium. Peeling and pulverization of the graphite layer caused by co-insertion of ions and electrolyte.
  • the coating material for the surface layer only the resin-based hard carbon precursor or the asphalt-based soft carbon precursor is used alone.
  • the main advantage of using resin as the coating material is that the resin has good fluidity at low temperature, not only can coat the surface, but also easily penetrate into the graphite particles through micropores in the graphite to improve the tap density and electrons of the graphite particles.
  • the conductivity is beneficial, and can also be cured by heating, introducing a catalyst or ultraviolet irradiation.
  • the resin will not melt and deform during the pyrolysis process, nor will it cause significant expansion, and the order of the amorphous carbon formed after pyrolysis of the resin is low.
  • the structure is relatively loose, and lithium ions can be relatively freely embedded and extracted therein without a large influence on the structure thereof, so that pulverization is less likely to occur.
  • the affinity of the resin material and the graphite is poor, so the carbon material obtained by pyrolysis thereof is not firmly bonded to the graphite, the carbon material obtained by pyrolysis of the resin has a low yield, is brittle, and has a large amount of volatiles during pyrolysis of the resin.
  • the specific surface area is high, the adhesion of the resin is strong, and the coated particles are easily bonded together, and the coating layer is easily broken during the heat treatment, and the resin has too many small molecules in the resin during the heat treatment.
  • excessive voids are formed on the surface of the coated material, resulting in an excessively large specific surface area of the coated graphite, resulting in an excessively large irreversible capacity for the first time.
  • the pitch pyrolysis carbon has a smaller specific surface area than the resin pyrolytic carbon coated graphite, has better affinity with graphite, and has a firmer structure, but the asphalt coating In the heating process, it is deformed by melting. If the amount is too much, the coated graphite particles are easily bonded to each other. If the amount is too small, the coating is not uniform, and the heating process is easy to expand, which affects the electrical properties of the graphite.
  • the present invention provides a method for doping a graphite fine powder as a negative electrode material, comprising the following steps:
  • Step A The “tailing material” produced in the production process of the lithium battery anode material is used as a raw material, a binder and a pore-forming agent are added, and kneading and granulation are carried out at a temperature higher than the softening point of the asphalt at 20 to 50° C., and then the roll is performed. Pressing or pressing, carbonizing at a high temperature of 800 to 1000 ° C;
  • Step B the carbonized material is pulverized and shaped to obtain spherical or elliptical graphite powder according to the particle size range; high temperature graphitization is performed at 2600 ° C or higher, and the pulverization/spheroidization process can be performed at the same time.
  • the collected "tails" are added to step A as a raw material for recycling;
  • Step C Performing particle size distribution on the graphitized powder, adding a certain proportion of graphite anode powder, and filling the gap between the particles by physical mixing to increase the bulk density.
  • the graphite powder is continuously vibrated by a tap density measuring instrument, and the bulk density of the powder can be measured.
  • the shape of the powder is close to a spherical shape or an elliptical shape, the contact between the powder particles is point contact or small-area contact, in which any void is left, and at the same time the limitations of the pulverization and spheroidizing equipment, the tap density of the powder is still Hard to improve.
  • By adding a certain amount of fine powder to the powder after the spheroidizing treatment it is filled into the voids, and the unit bulk density of the entire material can be further increased.
  • 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 electrolyte is embedded in the negative electrode, and the negative electrode is in a lithium-rich state;
  • 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 tailings produced in the production process of graphite anode materials have fine particles (D50 is generally 1-7 ⁇ m), high specific surface area (SSA ⁇ 10 m2/g), and low tap density (Tap ⁇ 0.6 g/cm3), although
  • the structure itself is a graphite layer structure with a certain capacity, but as a negative electrode material, it has the disadvantages of low volume specific energy, low capacity, poor material processing performance, etc. Therefore, the treatment method for tailings in the industry is mainly applied to steel metallurgy. Used as a recarburizer.
  • the market demand for graphite anode materials has also shown a rapid growth trend. As the output of anode materials continues to expand, the number of tailings increases, so the tailings are High value-added processing and recycling have a broad Market prospects.
  • the invention adopts the above technical solutions, and has the advantages that: 1.
  • the tailings produced in the industrial production of graphite anode materials have small particle size and large specific surface area, and the general treatment method in the industry is carried out as a refining agent with low added value. deal with. However, due to its small particle size, the channel resistance between lithium ions entering the graphite layer can be shortened, and the superior rate performance and low temperature performance are exhibited. 2.
  • bitumen and resin as binder kneading and granulating at a certain temperature, polymerizing small particles of graphite, and then rolling or pressing to make the internal structure further dense, increase its bulk density, and then carbonize at high temperature.
  • the asphalt and the resin form pyrolytic carbon, and the small molecules in the resin are formed into pores inside the material by the heat overflow, and these micropores are favorable for expanding the contact range of graphite and lithium ion deintercalation.
  • Graphitization transforms the interior of the material from the disordered overlap of the two-dimensional space to the orderly overlap of the three-dimensional space, which makes the structural structure of the material tend to be complete, further improving the cycle stability and product consistency of the material. 4.
  • Control the particle size Dmax of the product, the particle size index Dmax of the anode material powder is a very important technical parameter, especially in the application of automotive power battery, this index plays a very important role in the safety performance of the power battery.
  • the heating rate in step A is 1 to 10 ° C / min.
  • the raw material has a particle diameter D50 of 1 to 7 ⁇ m; a tap density of ⁇ 0.6 g/cm 3 and a specific surface area of ⁇ 10 m 2 /g.
  • the binder in the step A adopts modified asphalt
  • the modified asphalt adopts one or more of coal asphalt, petroleum asphalt, mesophase pitch and modified asphalt.
  • the pore forming agent in the step A is one or more of a phenol resin, an epoxy resin, a polyvinyl alcohol, a polyvinyl chloride resin, and a polyamide resin.
  • the weight ratio of graphite: binder: pore former in the step A is 100: 0.1 to 0.4: 0.01 to 0.1.
  • the particle size ratio is adjusted, and the weight ratio of the carbonized graphite to the added graphite powder is 1:0.05 to 0.2, wherein the added graphite powder has a smaller particle diameter than that obtained in the step B.
  • the average particle diameter D50 obtained after pulverization and spheroidization is 8 to 25 ⁇ m, and Dmax ⁇ 55.
  • tailings as raw materials saves the cost of raw materials.
  • the tailings particles are polymerized, and the defects such as low bulk density and high specific surface area are changed, and then rolling or Press to further increase its density.
  • the resin As a pore-forming agent, the resin has too many small molecules in the resin during the heat treatment process. Micropores are formed inside the material during the overflow process, and then the pulverization and shaping treatment can be used to obtain suitable particle size and isotropy of the anode material. Powder.
  • micropores facilitate the absorption and maintenance of the electrolyte, and the isotropic property has the advantage of co-intercalation with the PC electrolyte to ensure the performance of high and low temperature performance.
  • the added asphalt and resin are converted from disordered carbon layer structure to ordered structure, while improving the overall purity of the material, reducing its magazine content, ensuring batch consistency, increasing material cycle stability and Security performance.
  • the preparation method of the invention is safe and controllable, realizes the recycling of waste, and the prepared negative electrode material has good performance and exhibits good electrical properties.
  • Example 1 is a 500-fold scanning electron micrograph of the material prepared in Example 1.
  • Example 2 is a 1000x scanning electron micrograph of the material prepared in Example 1.
  • Example 3 is a 2000x scanning electron micrograph of the material prepared in Example 1.
  • Example 4 is a graph showing the tap density of the material prepared in Example 1.
  • Fig. 5 is a graph showing the rate discharge performance of a battery prepared by using the anode material of the present invention.
  • Fig. 6 is a graph showing the cycle retention ratio of a battery prepared by using the negative electrode material of the present invention.
  • Fig. 7 is a graph showing the high and low temperature discharge capacity retention ratio of a battery prepared by using the anode material of the present invention.
  • the high-temperature carbonized material is coarsely crushed and spheroidized to control the particle size Dmax of the material to obtain a powder having a particle diameter D50 of 16.52 ⁇ m, a tap density of 0.89 g/cm 3 and a specific surface area of 5.1 m 2 /g.
  • High temperature graphitization (2600 ° C) treatment further improve the material properties, the internal structure of the material from the disordered carbon to the ideal structure of graphite, tested (particle size D50 is 14.3 ⁇ m, tap density is 1.04g / cm 3, specific surface area 2.9 m2/g), finally, artificial graphite (particle diameter D50 of 11.3 ⁇ m, tap density of 1.10 g/cm 3 , specific surface area of 1.6 m 2 /g) was added in a ratio of 1:0.1, and finally, the present example was obtained.
  • the obtained negative electrode material was obtained.
  • the high-temperature carbonized material is coarsely crushed and spheroidized to control the particle diameter Dmax, and a powder having a particle diameter D50 of 12.71 ⁇ m, a tap density of 0.94 g/cm 3 and a specific surface area of 5.8 m 2 /g is obtained.
  • High temperature graphitization (2800 ° C) treatment further improve the material properties, the internal structure of the material from the disordered carbon to the ideal structure of graphite, tested (particle size D50 is 12.27 ⁇ m, tap density is 1.02g / cm 3, specific surface area 3.1m2/g), finally adding artificial graphite (particle diameter D50 of 10.31 ⁇ m, tap density of 1.10g/cm 3 , specific surface area: 1.9m2/g) at a ratio of 1:0.05, and finally obtaining the present embodiment.
  • the obtained negative electrode material is obtained negative electrode material.
  • the high-temperature carbonized material is coarsely crushed and spheroidized to control the particle diameter Dmax, and a powder having a particle diameter D50 of 15.92 ⁇ m, a tap density of 0.93 g/cm 3 and a specific surface area of 3.2 m 2 /g is obtained.
  • High temperature graphitization (2600 °C) treatment further improve the material properties, and transform the internal structure of the material from disordered carbon to graphite ideal structure.
  • the particle size D50 is 15.35 ⁇ m, the tap density is 0.98g/cm 3 , and the specific surface area 2.7 m2/g), and finally artificial graphite (particle diameter D50 of 11.3 ⁇ m, tap density of 1.10 g/cm 3 , specific surface area of 1.6 m 2 /g) was mixed at a ratio of 1:0.09 to finally obtain the present example.
  • the obtained negative electrode material was 15.35 ⁇ m, the tap density is 0.98g/cm 3 , and the specific surface area 2.7 m2/g), and finally artificial graphite (particle diameter D50 of 11.3 ⁇ m, tap density of 1.10 g/cm 3 , specific surface area of 1.6 m 2 /g) was mixed at a ratio of 1:0.09 to finally obtain the present example.
  • the obtained negative electrode material was obtained.
  • 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 4.
  • the production of the 4244130 soft-packed finished battery was used for the detection of the rate charge and discharge.
  • Example 1 of the present invention a scanning electron micrograph of the negative electrode material obtained in Example 1 of the present invention can be seen from FIG. 4, and the tap density of the material is as high as 1.28 g/cm 3 , which is known from FIG. 5 and is prepared from the material.
  • Power The high-rate discharge of the battery is 50C/1C, and the capacity retention rate is 89.61%.
  • the battery 2C charge and discharge 3800 times capacity retention rate is 81.91%.
  • the high-low temperature performance of the battery, -40 ° C The discharge efficiency can reach 82.3%. It can be seen from the above that the materials prepared by the invention have excellent performance in various aspects, can meet the requirements of various aspects of the power battery of the new energy vehicle, and have broad market prospects.

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Abstract

本发明提供一种石墨细粉作为锂离子电池负极材料的循环利用方法，包括以下几个步骤：步骤A：将锂电池石墨负极材料生产过程中所产生的"尾料"作为原料，加入粘结剂、造孔剂，在一定温度下进行捏合造粒，再进行辊压或压制，在高温下进行碳化；步骤B：将碳化后的材料进过粉碎、整形球化，得到符合粒径范围要求的球形或椭圆形石墨粉体，再进行高温石墨化，同时将粉碎/球化过程中再次收集的"尾料"添加到步骤A中作为原料循环使用；步骤C：对球化处理后的粉体进行粒度调配，填充到颗粒之间的缝隙。本发明制备方法工艺安全、可控，实现了低价值石墨"尾料"的循环利用，且制得的负极材料性能良好，表现出良好的循环、倍率充放和低温性能。

Description

一种石墨细粉作为锂离子电池负极材料的循环利用方法 技术领域
本发明属于能源领域，涉及一种负极材料的方法，尤其涉及一种以石墨负极材料生产过程中产生的超细石墨粉体—“尾料”为原料，通过处理进行循环再利用，用作锂离子电池负极材料的方法。
背景技术
随着汽车行业的发展，石油、天然气等不可再生石化燃料的耗竭日益受到关注，空气污染和室温效应也成为全球性的问题。为解决能源问题，实现低碳环保，基于目前能源技术的发展水平，电动汽车技术逐渐成为全球经济发展的重点方向，美国、日本、德国、中国等国家相继限制燃油车使用，大力发展电动车。作为电动汽车的核心部件——动力电池也迎来了大好的发展机遇。动力电池是指应用于电动车的电池，包括锂离子电池、铅酸电池、燃料电池等，其中，锂离子电池因具有比能量高、比功率大、自放电少、使用寿命长及安全性好等优点，已成为目前各国发展的重点。而作为锂离子电池负极材料的石墨类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。
石墨作为一种战略资源，不仅普遍应用于一般工业和消费领域，还广泛用于一些特殊的工业领域。但目前日益扩大的市场需求所导致的低端化无序开发，对我国的资源保护和产业升级造成不利影响。石墨作为负极材料在生产过程中，都需要经过粉碎机将石墨原料进行多次粉碎后，再通过球化机对其进行多次球化。采用此种工艺，具有原材料利用率低、环境差等缺点，由于每次粉碎和球化都需要通过分级后收得中间半成品再进行下次处理，而每次分级都将降低原材料的利用率，所以此种负极材料的生产方式最终的成品率一半为40％～50％。剩余的50％～60％就成了“尾料”，石墨细粉—“尾料”其粒径小，比表面积高、振实密度低，不能再用作锂离子电池负极材料，因此利用价值极低，主要用于钢铁冶金等方面作为增碳剂使用，这样不仅增加了生产成本，还造成了资源的浪费。
同时，针对石墨的各种传统改性方式，主要以表面碳包覆为主，通过在石墨表层包覆一层热解碳，能有效地阻止有机溶剂与石墨本体的作用，从而防止了锂 离子与电解液的共插所引起的石墨层剥落与粉化。而作为表层的包覆材料均只单独采用树脂类硬炭前躯体或者是沥青类软炭前躯体。
采用树脂类作为包覆材料，主要优点是树脂在低温下流动性好，不仅能包覆表面，而且很容易通过石墨内的微孔渗入到石墨颗粒内部，对提高石墨颗粒的振实密度和电子电导率有益，还可以通过加热、引入催化剂或紫外线照射等方法固化，树脂热解过程中不会熔化变形，也不会产生明显膨胀，树脂热解后形成的无定形碳的有序度低，结构比较松散，锂离子能相对自由地在其中嵌入和脱出而不会对其结构产生大的影响，因此不容易发生粉化。但是，树脂类材料和石墨的亲和力较差，因此他们热解得到的炭材料和石墨结合不牢固，由树脂热解得到的炭材料得率偏低，具有脆性，树脂热解过程中挥发份多，比表面积偏高，树脂的粘结力较强，易于造成包覆颗粒粘接在一起，热处理后粉碎时易造成包覆层的破坏，同时树脂在热处理过程中，树脂内的小分子过多，在溢出过程中会造成包覆后材料的表面产生过多的空隙，导致包覆后的石墨的比表面积过大而造成首次不可逆容量过大。
以上这些问题，影响了树脂包覆石墨材料的循环效率、循环稳定性和石墨电极的压缩性。而采用沥青、石油焦油、煤焦油或它们的混合物包覆石墨，沥青热解炭比树脂热解炭包覆石墨的比表面积小，和石墨的亲合性要好，结构更牢固，但沥青包覆在加热过程中因熔化而变形，用量过多也易造成包覆石墨颗粒的相互粘接，用量过少易造成包覆不均匀，并且加热过程中易于膨胀，影响石墨的电性能。
发明内容
为了解决以上技术问题，本发明提供一种石墨细粉掺杂处理用作负极材料的方法，包括以下几个步骤：
步骤A：将锂电池负极材料生产过程中所产生的“尾料”为原料，加入粘结剂、造孔剂，在高于沥青软化点温度20～50℃下进行捏合造粒，再进行辊压或压制，在高温800～1000℃下进行碳化；
步骤B:将碳化后的材料进过粉碎、整形球化，得到符合粒径范围要求的球形或椭圆形石墨粉体；在2600℃以上进行高温石墨化，同时可将粉碎/球化过程中所收集的“尾料”添加到步骤A作为原料循环使用；
步骤C：对石墨化处理后的粉体进行粒度调配，添加一定比例的石墨负极粉体，通过物理混合的方式填充到颗粒之间的缝隙，提高其体积密度。
其中，石墨粉体通过振实密度测量仪，不断振动，可测得粉体的堆砌密度。但是由于粉体形状接近球形或者椭圆形，粉体颗粒之间的接触为点接触或者小面积接触，其中任然留有空隙，同时粉碎和球化设备的局限性，粉体的振实密度仍难以提升。通过在整形球化处理后粉体中添加一定量的细粉，填充到空隙中，可进一步提高材料整体的单位体积密度。
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—脱出而形成层间插入式化合物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。
而石墨负极材料生产过程中产生的尾料，其颗粒细(D50一般为1～7μm)，比表面积高(SSA≥10㎡/g)、振实密度低(Tap≤0.6g/cm3)，虽然其本身结构为石墨层状结构，具有一定容量，但是其作为负极材料，具有体积比能量低、容量发挥低、材料加工性能差等缺点，因此行业内针对尾料的处理方式主要应用于钢铁冶金等方面作为增碳剂使用。但随着电动汽车的不断推广和快速发展，石墨负极材料的市场需要也呈现快速增长的态势，在负极材料产量不断扩大的同时，尾料的数量规模也随之增多，因此，对尾料进行高附加值处理和回收利用具有广阔 的市场前景。
本发明采用以上技术方案，其优点在于，1、工业生产石墨负极材料中所产生的尾料，粒径小，比表面积大，行业内通用的处理方式是作为附加值很低的增碳剂进行处理。但正由于其粒径小，所以可以缩短锂离子进入石墨层间的通道阻力，表现出更加优异的倍率性能和低温性能。2、添加沥青和树脂作为粘合剂，在一定温度下进行捏合造粒，将石墨小粒子聚合，再通过辊压或者压制，让内部结构进一步缜密，提高其体积密度，接着在高温下进行碳化，沥青和树脂形成热解碳，同时树脂中的小分子受热溢出中在材料内部形成孔隙，这些微孔有利于扩大石墨和锂离子脱嵌的接触范围。3、石墨化使材料内部从二维空间的无序重迭转变为三维空间的有序重迭，让材料结构结构趋于完整，进一步提高材料的循环稳定性和产品一致性。4.控制产品的粒径Dmax，负极材料粉体中粒度指标Dmax是一个非常关键的技术参数，尤其在应用于汽车动力电池方面，该指标对动力电池的安全性能起到非常关键的作用。如果材料粉体中存在粒径偏大的石墨颗粒，在动力电池快速充电过程中，由于锂离子进入石墨层间的通道增加，而嵌入电流过大，会造成表面析锂，形成枝晶，刺穿隔膜，造成安全隐患。5、后期再通过粒度调配，避免了材料通过单纯机械处理导致振实密度难以进一步提升的难题，提高其体积能量密度。
优选的，步骤A中升温速率1～10℃/min。
优选的，所述原料的粒径D50为1～7μm；振实密度≤0.6g/cm3，比表面积≥10㎡/g。
优选的，步骤A中粘结剂采用改质沥青，所述改质沥青采用煤沥青、石油沥青、中间相沥青、改质沥青中的一种或几种。
优选的，步骤A中造孔剂为酚醛树脂、环氧树脂、聚乙烯醇、聚氯乙烯树脂、聚酰胺树脂的一种或几种。
优选的，所述步骤A中石墨：粘结剂：造孔剂的重量比为100:0.1～0.4:0.01～0.1。优选的，所述步骤C中粒度调配，碳化后的石墨与添加的石墨粉体的重量比为1:0.05～0.2，其中，添加的石墨粉体粒径小于步骤B中所得到的粉体。
所述步骤B中，粉碎、整形球化后得到的平均粒径D50为8～25μm，Dmax≤55。
动力电池作为新能源汽车的核心组成部分，较日常生活中使用的普通锂离 子电池，对材料具有更为严苛的标准和要求，如高倍率充放电性能、良好的高低温性能、超长循环性能、高安全性能和较低成本等。而尾料正是由于其具有较小的粒径，锂离子进出石墨层间的路径减少，因此其本身具有非常优异的倍率充放性能。
使用尾料为原料，节省了原材料成本，通过对尾料进行“造粒”，添加沥青作为粘合剂，使尾料粒子聚合，改变其体积密度低、比表面积高等缺点，再进行辊压或压制，进一步提高其密度。树脂作为造孔剂，在热处理过程中，树脂内的小分子过多，在溢出过程中在材料内部形成微孔，再经过粉碎和整形处理后可得到可用于负极材料合适粒径、各向同性的粉体。微孔便于电解液的吸收和保持，各向同性具有抗PC电解液共嵌的优势，保证高低温性能的发挥。高温石墨化后，使添加的沥青和树脂，从无序碳层结构向有序结构转换，同时提高材料整体的纯度，降低其杂志含量，保证批次的一致性，增加材料的循环稳定性和安全性能。
本发明制备方法工艺安全、可控，实现了废物的循环利用，且制得的负极材料性能良好，表现出很好的电性能。
附图说明
图1是实施例1所制备的材料500倍扫描电镜图。
图2是实施例1所制备的材料1000倍扫描电镜图。
图3是实施例1所制备的材料2000倍扫描电镜图。
图4是实施例1所制备的材料振实密度曲线图。
图5是采用本发明负极材料所制备的电池的倍率放电性能图。
图6是采用本发明的负极材料所制备的电池的循环保持率图。
图7是采用本发明负极材料所制备的电池的高低温放电容量保持率图。
具体实施方式
下面结合附图，对本发明的较优的实施例作进一步的详细说明：
实施例1
以100Kg人造石墨“尾料”(粒径D50＝3.46μm，振实密度0.47g/cm3，比表面积15.6㎡/g)为原料，按石墨：沥青：造孔剂＝100:0.2:0.05的比例，称取0.2Kg的改质煤沥青(软化点120℃)，0.05Kg的环氧树脂(软化点80℃)，一起投入到带有加热装置的捏合机中，在混合的同时，将捏合机升温至140℃(比 沥青软化点高20℃)。一起混合120min，然后用混捏好的物料通知压片机进行压制，提高其体积密度。将压制后的物料在惰性气体保护下，以10℃/min的升温速率升至900℃，并保温一小时，然后降温至室温。
高温碳化后的物料通过粗碎、整形球化，控制材料的粒径Dmax，得到粒径D50为16.52μm，振实密度为0.89g/cm3，比表面积5.1㎡/g的粉体，再通过高温石墨化(2600℃)处理，进一步提高材料性能，使材料内部结构由无序碳向石墨理想结构转换，经检测(粒径D50为14.3μm，振实密度为1.04g/cm3，比表面积2.9㎡/g)，最后以1:0.1的比例添加人造石墨(粒径D50为11.3μm，振实密度为1.10g/cm3，比表面积1.6㎡/g)进行混合，最终得到本实施例所制得的负极材料。
实施例1物理性能检测如表1所示：
表1
Figure PCTCN2015085813-appb-000001
实施例2
以100Kg人造石墨“尾料”(粒径D50＝2.31μm，振实密度0.37g/cm3，比表面积18.6㎡/g)为原料，按重量比石墨：沥青：造孔剂＝100:0.1:0.1的比例，称取0.1Kg的改质煤沥青(软化点150℃)，0.1Kg的酚醛树脂(软化点110℃)，一起投入到带有加热装置的捏合机中，在混合的同时，将捏合机升温至170℃。一起混合140min，然后用混捏好的物料通知压片机进行压制，提高其体积密度。将压制后的物料在惰性气体保护下，以5℃/min的升温速率升至950℃，并保温 一小时，然后降温至室温。
高温碳化后的物料通过粗碎、整形球化，控制材料的粒径Dmax，得到粒径D50为12.71μm，振实密度为0.94g/cm3，比表面积5.8㎡/g的粉体，再通过高温石墨化(2800℃)处理，进一步提高材料性能，使材料内部结构由无序碳向石墨理想结构转换，经检测(粒径D50为12.27μm，振实密度为1.02g/cm3，比表面积3.1㎡/g)，最后以1:0.05的比例添加人造石墨(粒径D50为10.31μm，振实密度为1.10g/cm3，比表面积1.9㎡/g)进行混合，最终得到本实施例所制得的负极材料。
实施例2物理性能检测如表2所示：
表2
Figure PCTCN2015085813-appb-000002
实施例3
以100Kg人造石墨“尾料”(粒径D50＝6.16μm，振实密度0.59g/cm3，比表面积14.54㎡/g)为原料，按重量比石墨：沥青：造孔剂＝100:0.4:0.1的比例，称取0.4Kg的改质煤沥青(软化点100℃)，0.1Kg的聚酰胺树脂(软化点80℃)，一起投入到带有加热装置的捏合机中，在混合的同时，将捏合机升温至130℃。一起混合150min，然后用混捏好的物料通知压片机进行压制，提高其体积密度。将压制后的物料在惰性气体保护下，以10℃/min的升温速率升至1000℃，并保温半小时，然后降温至室温。
高温碳化后的物料通过粗碎、整形球化，控制材料的粒径Dmax，得到粒径D50为15.92μm，振实密度为0.93g/cm3，比表面积3.2㎡/g的粉体，再通过高温石墨化(2600℃)处理，进一步提高材料性能，使材料内部结构由无序碳向石墨理想结构转换，经检测(粒径D50为15.35μm，振实密度为0.98g/cm3，比表面积2.7㎡/g)，最后以1:0.09的比例添加人造石墨(粒径D50为11.3μm，振实密度为1.10g/cm3，比表面积1.6㎡/g)进行混合，最终得到本实施例所制得的负极材料。
实施例3物理性能检测如表3所示：
表3
Figure PCTCN2015085813-appb-000003
电化学性能测试
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，用以上实施例和比较例的负极材料：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4。
表4
Figure PCTCN2015085813-appb-000004
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。
用上实施例和比较例的负极材料：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3。
表3
Figure PCTCN2015085813-appb-000005
另外，由图1～3可知，本发明实施例1得到的负极材料的扫描电镜图，由图4可知，该材料的振实密度高达1.28g/cm3，由图5可知，由该材料制备的动力 电池，其高倍率放电50C/1C，容量保持率为89.61％，由图6可知，电池2C充放电3800次容量保持率为81.91％，由图7可知，电池的高低温性能图，-40℃放电效率可达82.3％。由上可知，本发明所制备的材料，各方面性能优异，可满足新能源汽车动力电池各方面的指标要求，具有广阔的市场前景。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。

Claims (8)

  1. 一种石墨细粉作为锂离子电池负极材料的循环利用方法，其特征在于，包括以下几个步骤：
    步骤A：将锂电池负极材料生产过程中所产生的“尾料”为原料，加入粘结剂、造孔剂，在高于沥青软化点温度20～50℃下进行捏合造粒，再进行辊压或压制，在高温800～1000℃下进行碳化；
    步骤B:将碳化后的材料进过粉碎、整形球化，得到符合粒径范围要求的球形或椭圆形石墨粉体；在2600℃以上进行高温石墨化，同时可将粉碎/球化过程中所收集的“尾料”添加到步骤A作为原料循环使用；
    步骤C：对石墨化处理后的粉体进行粒度调配，添加一定比例的石墨负极粉体，通过物理混合的方式填充到颗粒之间的缝隙，提高其体积密度。
  2. 如权利要求1所述的方法，其特征在于，所述原料的粒径D50为1～7μm；振实密度≤0.6g/cm3，比表面积≥10㎡/g。
  3. 如权利要求1所述的方法，其特征在于，所述步骤B中粉碎、整形球化后得到的粉体平均粒径D50为8～25μm，Dmax≤55。
  4. 如权利要求1所述的方法，其特征在于，所述步骤A中粘结剂采用改质沥青，所述改质沥青采用煤沥青、石油沥青、中间相沥青、改质沥青中的一种或几种。
  5. 如权利要求1所述的方法，其特征在于，所述步骤A中造孔剂为酚醛树脂、环氧树脂、聚乙烯醇、聚氯乙烯树脂、聚酰胺树脂的一种或几种。
  6. 如权利要求1所述的方法，其特征在于，所述步骤A中石墨：粘结剂：造孔剂的重量比为100:0.1～0.4:0.01～0.1。
  7. 如权利要求1所述的方法，其特征在于，所述步骤C中粒度调配，碳化后的石墨与添加的石墨粉体的重量比为1:0.05～0.2，其中，添加的石墨负极粉体粒径小于步骤B中粉碎、整形球化后得到的粉体。
  8. 如权利要求1所述的方法，其特征在于，所述步骤A中升温速率1～10℃/min。
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CN107799773A (zh) * 2017-09-26 2018-03-13 湖南湘讯企业管理有限公司 一种锂电池用负极材料及其制备方法和应用
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CN115036490A (zh) * 2022-07-01 2022-09-09 内蒙古三信科技发展有限公司 一种具有耐低温性能的免炭化负极材料及其制备方法
CN115275416A (zh) * 2022-08-08 2022-11-01 江苏正力新能电池技术有限公司 废旧锂离子电池中石墨的回收方法及高容快充负极材料
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CN118136841A (zh) * 2024-05-10 2024-06-04 四川金汇能新材料股份有限公司 一种利用粉碎尾料制备的软碳复合负极材料及制备方法

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