WO2017024898A1 - 一种高容量锡碳负极材料的制备方法 - Google Patents

一种高容量锡碳负极材料的制备方法 Download PDF

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WO2017024898A1
WO2017024898A1 PCT/CN2016/086703 CN2016086703W WO2017024898A1 WO 2017024898 A1 WO2017024898 A1 WO 2017024898A1 CN 2016086703 W CN2016086703 W CN 2016086703W WO 2017024898 A1 WO2017024898 A1 WO 2017024898A1
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resin
tin
anode material
asphalt
powder
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PCT/CN2016/086703
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French (fr)
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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 the field of lithium ion batteries, in particular to a method for preparing a tin carbon anode material for a negative electrode of a lithium ion battery, wherein the tin carbon anode material prepared by the method is coated with a composite material formed of asphalt and resin to coat the tin powder. To improve its cycle performance.
  • lithium-ion batteries have developed rapidly.
  • the commercial lithium ion battery anode material is made of graphite-based carbon material, has low lithium insertion/deintercalation potential, suitable reversible capacity, rich resources, and low price, and is an ideal anode material for lithium ion batteries.
  • 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.
  • 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.
  • 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.
  • the amorphous carbon formed by pyrolysis of the resin-based polymer has a low degree of order and a loose structure, and lithium ions can be relatively freely embedded and extracted therein without a large influence on the structure thereof.
  • tin is one of the most promising anode materials for carbon materials because tin has a high specific gravity capacity of up to 994 mAh/g; and has a smooth discharge platform similar to graphite.
  • extensive research has been carried out on such materials and some progress has been made.
  • 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.
  • 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. These methods can indeed improve the cycle performance of tin to a certain extent, but the degree of improvement is limited, and the cycle performance of the material still cannot meet the needs.
  • the resin hard carbon precursor or the asphalt soft carbon precursor is coated separately.
  • the main advantage of using resin as the coating material is that the resin has good fluidity at low temperature, can not only coat the surface, but also easily penetrates into the material particles through the micropores, which is beneficial to improve the tap density and electronic conductivity of the material. It can also be cured by heating, introduction of catalyst or ultraviolet irradiation. The resin will not melt and deform during the pyrolysis process, and will not cause significant expansion. However, there are also some problems, mainly: the yield of carbon materials obtained by pyrolysis of the resin.
  • Asphalt, petroleum tar, coal tar or a mixture thereof is used as a coating material, and the pitch pyrolysis carbon has a smaller specific surface area than the resin pyrolysis carbon coating, and the material The affinity is better, the structure is firmer, but the asphalt coating is deformed by melting during the heating process. If the amount is too much, the particles of the coating material are easily bonded to each other. If the amount is too small, the coating may be uneven and heated. It is easy to expand during the process and affects the electrical properties of the material.
  • the technical problem to be solved by the present invention is to provide a method for preparing a high-capacity tin-carbon anode material to solve the problems raised in the above background art.
  • a preparation method of a high-capacity tin-carbon anode material the preparation steps are as follows:
  • tin powder the weight of the dispersion solvent is 1:0.05-0.15:0.2-0.6, the tin powder and the dispersing solvent are weighed, the tin powder is added to the dispersing solvent, and the ultrasonic dispersion is evenly distributed. Adding to the mixed liquid in step 2, stirring until the components are uniformly mixed;
  • step 3 The liquid uniformly mixed in step 3 is atomized and cooled by an atomizing device, and the powder obtained by atomization is collected and classified to obtain a powder having an average particle diameter of 5 to 30 ⁇ m.
  • the resin has been cured;
  • step 4 The powder obtained in step 4 is heated to 700-900 ° C at a rate of 1 to 10 ° C / min under the protection of an inert gas, and then kept for 1 to 5 hours, naturally cooled, and after cooling, a high-capacity tin is obtained. Carbon anode material.
  • the asphalt described in the step 1 includes one or more mixtures of coal tar pitch, petroleum pitch, modified pitch, mesophase pitch, and condensed polycyclic polynuclear aromatic hydrocarbon obtained by upgrading the pitch.
  • the softening point is above 100 °C.
  • the resin described in the step 1 is a thermoplastic resin, and one or a mixture of one or more of a furan resin, a urea resin, a pyrimidine resin, a phenol resin, an epoxy resin, and a polyoxymethylene acrylate resin.
  • the stirring time described in the step 1 is 80 to 130 minutes, and the final temperature of the heating is 30 to 40 ° C higher than the highest softening point of the pitch and the resin in the component.
  • the curing agent described in the step 2 is hexamethylenetetramine, diethylaminopropylamine, trimethylhexamethylenediamine, dihexyltriamine, and a thermosetting resin having a curing action.
  • a thermosetting resin having a curing action.
  • the tin powder described in the step 3 has an average particle diameter of ⁇ 100 nm.
  • the dispersion solvent described in the step 3 is one of ethanol, isopropanol, carbon disulfide, toluene, xylene or distilled water with a dispersion medium.
  • the atomization in the step 4 is one of the atomization devices that operate by the principles of ultrasonic atomization, centrifugal atomization, and high pressure atomization.
  • the classification treatment in the step 4 is a combination of one or both of cyclone separation and sieving treatment of the powder.
  • the inert gas is a mixture of one or both of nitrogen, argon and helium.
  • the most prominent innovation of the present invention is that the cladding material precursor is composited and then coated with tin powder; the uniformity of mixing of the precursor materials of various coating materials is ensured, and no solvent is required, and the environment is friendly; In addition, the process is simple, the cost is low, and the industrial production is easy;
  • the invention adds a certain amount of resin curing agent to the composite material, and after curing, the resin can play a skeleton supporting role to prevent the asphalt from melting during the carbonization process and causing the powder to form a sticky joint block after the carbonization, and it is necessary to The phenomenon of breaking the material coating caused by the crushing treatment;
  • the amorphous carbon formed by the high-temperature carbonization of the resin has strong corrosion resistance to the electrolyte.
  • the interlayer spacing of the amorphous carbon is large, and the lithium ions can enter and exit quickly, satisfying the high-rate charge and discharge of the lithium ion battery.
  • the requirement is that the holes and voids formed by the carbonization of the resin can buffer the volume effect of the tin powder during charging and discharging, and ensure the overall stability of the material;
  • the invention has obvious superiority as the coating material of the resin-based hard carbon precursor or the asphalt-based soft carbon precursor, and the asphalt carbon and the resin carbon are pinned together, and the complementation is insufficient. Effectively increase the strength of the coating to ensure the cycle stability of the tin-carbon composite.
  • the mesophase pitch (softening point 250 ° C) and the phenolic resin (softening point 110 ° C) were added together in a ratio of 1:3 (3.5 Kg and 10.5 Kg) to a 20 L kneading kettle, and the temperature was raised and heated to 300 ° C.
  • tin powder The weight of the dispersing solvent is 1:0.1:0.3, and 1.4Kg of tin powder having an average particle diameter of 50 nm and 5.2 kg of an alcohol solution are weighed, and the tin powder is added to the alcohol solution, and then dispersed by an ultrasonic device, and dispersed.
  • the performance of the negative electrode material of the lithium ion battery of Example 1 was examined and tested by the half-cell test method.
  • the negative electrode material of the lithium ion battery prepared in Example 1 was: acetylene black: PVDF (polyvinylidene fluoride) weight ratio of 93:3:4
  • NMP N-methylpyrrolidone
  • LiPF6/EC+DEC+DMC 1:1:1
  • the polypropylene microporous membrane is a membrane and assembled into a battery.
  • the charge-discharge voltage is 0-2.0V, and the charge-discharge rate is 0.2C.
  • the battery performance can be tested.
  • the initial discharge capacity of the electrode material is 445mAh/g, and the capacity after 100 cycles is still 412mAh/g. 92.6%.
  • the mesophase pitch (softening point 250 ° C) and the phenolic resin (softening point 110 ° C) were added together in a ratio of 1:4 (3 Kg and 12 Kg) to a 20 L kneading kettle, and the heating was started to be heated to 300 ° C in the asphalt and After the resin is melted into a liquid, 0.48 Kg of a curing agent, hexamethylenetetramine, is added in a proportion of 4% by weight of the resin, and stirring is continued until the components are uniformly mixed; according to the total weight of the asphalt and the resin: tin powder: dispersing solvent The weight of 1:0.09:0.27 is weighed 1.35Kg of tin powder with an average particle size of 50nm and 4.05kg of xylene solution.
  • the tin powder is added to the xylene solution, and then dispersed by an ultrasonic device. Adding a mixed liquid of uniformly mixed asphalt, resin and curing agent, stirring for 150 minutes, then spraying and cooling by a centrifugal atomizing device, and collecting a powder having an average particle diameter of 5 to 30 ⁇ m through a cyclone separator, and then The mixture was heated to 850 ° C under nitrogen atmosphere, kept for 3 hours, and then cooled to room temperature to finally obtain a high-capacity tin carbon battery anode material.
  • the performance of the negative electrode material of the lithium ion battery of Example 2 was examined by the same detection method as in Example 1.
  • the initial discharge capacity of the motor material was 416 mAh/g, and the capacity after 100 cycles was still 379 mAh/g. 91.1%.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Abstract

一种高容量锡碳负极材料的制备方法，通过将包覆材料前驱体复合处理后，再添加一定量的树脂固化剂，然后和锡粉混合均匀后通过雾化、碳化处理，使复合包覆材料对锡粉进行全覆盖；其次树脂经过固化后，可以起到骨架支撑作用，防止碳化过程中沥青发生融并导致材料碳化后出现粘连结块，而需要对其进行破碎处理致使包覆层破坏的现象。采用本发明的方法保证了多种包覆材料前驱体混合的均匀性，工艺简单，成本低，易工业化生产。

Description

一种高容量锡碳负极材料的制备方法 技术领域
本发明涉及锂离子电池领域，具体为一种用于锂离子电池负极的锡碳负极材料的制备方法，该方法制备的锡碳负极材料采用沥青和树脂形成的复合材料对锡粉进行包覆处理，以改善其循环性能。
背景技术
自从1990年日本索尼公司率先研制成功锂离子电池并将其商品化以来，锂离子电池得到了迅猛发展。如今锂离子电池已经广泛地应用于民用及军用的各个领域。随着科技的不断进步，人们对电池的性能提出了更多更高的要求：电子设备的小型化和个性化发展，需要电池具有更小的体积和更高的比能量输出；航空航天能源要求电池具有循环寿命，更好的低温充放电性能和更高的安全性能；电动汽车需要大容量、低成本、高稳定性和安全性能的电池。
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。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。而树脂类聚合物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。
另外，锡是一种最有希望取代碳材料的负极材料，这是因为锡具有高达994mAh/g的高克比容量；并且具有类似于石墨的平稳的放电平台。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。这些方法确实能在一定程度上改善锡的循环性能，但改善的程度有限，材料的循环性能依然不能满足需要。
以上显示，目前对材料的包覆改性处理中，均只单独包覆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，而且很容易通过微孔渗入到材料颗粒内部，对提高材料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，但也存在一些问题，主要有：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。以上这些问题，影响了树脂包覆材料的循环效率、循环稳定性和电极的压缩性。采用沥青、石油焦油、煤焦油或它们的混合物作为包覆材料，沥青热解炭比树脂热解炭包覆的比表面积小，和材料 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材料颗粒的相互粘接，用量过少易造成包覆不均匀，并且加热过程中易于膨胀，影响材料的电性能。
发明内容
本发明所解决的技术问题在于提供一种高容量锡碳负极材料的制备方法，以解决上述背景技术中提出的问题。
一种高容量锡碳负极材料的制备方法，其制备步骤如下：
1、将软化点在100℃～300℃之间的沥青和软化点在50℃～150℃之间的树脂按1：1.5～4的重量比加入到具有加热和搅拌装置的捏合釜中，以10～40℃/min的速率加热升温至沥青和树脂均熔化成液体；
2、然后加入占树脂量2％～5％的固化剂，在惰性气体保护下，不断搅拌至各种组分混合均匀；
3、按照树脂和沥青总重量：锡粉：分散溶剂的重量为1:0.05～0.15：0.2～0.6的比例称取锡粉和分散溶剂，将锡粉加入到分散溶剂中，并超声分散均匀后加入到步骤2中的混合液体中，搅拌至各组分混合均匀；
4、将步骤3中混合均匀的液体通过雾化装置雾化冷却，再对雾化所得的粉体进行收集并进行分级处理，得到平均粒径介于5～30μm之间的粉体，此时树脂已完成固化；
5、将步骤4中所得到的粉体在惰性气体的保护下，以1～10℃/min的速度升温至700～900℃，再保温1～5h，自然降温，冷却后即得到高容量锡碳负极材料。
本发明中，步骤1中所述的沥青包括煤沥青、石油沥青、改质沥青、中间相沥青、由沥青改质而得到的缩合多环多核芳香烃中的一种或一种以上的混合物，软化点在100℃以上。
本发明中，步骤1中所述的树脂为热塑性树脂，包括呋喃树脂、脲醛树脂、嘧胺树脂、酚醛树脂、环氧树脂和聚甲醛丙烯酸甲酯树脂中的一种或一种以上的混合物。
本发明中，步骤1中所述的搅拌的时间为80～130min，加热的最终温度比组分中沥青和树脂的最高软化点高30～40℃。
本发明中，步骤2中所述的固化剂为六次甲基四胺、二乙胺基丙胺、三甲基六亚甲基二胺、二已基三胺、具有固化作用的热固性树脂中的一种或一种以上的混合物。
本发明中，步骤3中所述的锡粉的平均粒径≤100nm。
本发明中，步骤3中所述的分散溶剂为乙醇、异丙醇、二硫化碳、甲苯、二甲苯或者带有分散介质的蒸馏水中的一种。
本发明中，步骤4中雾化采用的是利用超声雾化、离心雾化、高压雾化原理工作的雾化装置中的一种。
本发明中，步骤4中分级处理采用的是对粉体进行旋风分离、过筛处理中的一种或两者的结合。
在上述的制备方法中，所述的惰性气体为氮气、氩气、氦气中的一种或两种的混合气。
与现有技术，本发明的有益效果是：
1、本发明最突出的创新点是将包覆材料前驱体复合处理后，再包覆锡粉；保证了多种包覆材料前驱体混合的均匀性，同时不需要任何溶剂，对环境友好；另外，工艺简单，成本低，易工业化生产；
2、本发明通过对复合材料添加一定量的树脂固化剂，树脂经过固化后，可以起到骨架支撑作用，防止碳化过程中沥青发生融并导致碳化后粉体出现粘连结块，而需要对其进行破碎处理致使材料包覆层破坏的现象；
3、树脂经过高温碳化后形成的无定形碳，对电解液具有较强的抗腐蚀性能力，同时，无定形炭的层间距较大，锂离子能快速进出，满足锂离子电池高倍率充放电的要求，其次树脂碳化后形成的孔洞和空隙能够缓冲锡粉在充放电时产生的体积效应，保证材料的整体稳定性能；
4、本发明与单独包覆树脂类硬炭前躯体或者沥青类软炭前躯体的作为包覆材料相比，具有明显的优越性，沥青炭和树脂炭相互钉扎在一起，互补不足，能有效提高包覆层的强度，保证锡碳复合材料的循环稳定性。
具体实施方式
为了使本发明的技术手段、创作特征、工作流程、使用方法达成目的与功效易于明白了解，下面进一步阐述本发明。
实施例1
将中间相沥青(软化点250℃)和酚醛树脂(软化点110℃)按照1：3(3.5Kg和10.5Kg)的比例一起加入到在20L的捏合釜中，开始升温加热到300℃，在沥青和树脂均熔化成液体后，然后按照树脂重量3％的比例添加0.315Kg的固化剂—六次甲基四胺，不断搅拌至各组分混合均匀；按照沥青和树脂总重量：锡粉：分散溶剂的重量为1:0.1：0.3的比例称取1.4Kg平均粒径为50nm的锡粉和5.2公斤的酒精溶液，将锡粉加入到酒精溶液后，通过超声波装置进行分散，分散均有后，加入已混合均匀的沥青、树脂、固化剂的混合液体中，搅拌120min后通过超声雾化装置喷洒冷却，并通过旋风分离器收集平均粒径介于5～30μm之间的粉体，然后在氮气保护下加热至850℃，保温3小时，然后冷却至室温，最终得到高容量锡碳电池负极材料。
检验实施例1锂离子电池负极材料的性能，用半电池测试方法进行测试，用实施例1制备的锂离子电池负极材料:乙炔黑:PVDF(聚偏氟乙烯)重量比为93:3:4，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的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，该电极材料的首次放电容量达445mAh/g，100次循环后的容量仍有412mAh/g，保持率为92.6％。
实施例2
将中间相沥青(软化点250℃)和酚醛树脂(软化点110℃)按照1：4(3Kg和12Kg)的比例一起加入到在20L的捏合釜中，开始升温加热到300℃，在沥青和树脂均熔化成液体后，然后按照树脂重量4％的比例添加0.48Kg的固化剂—六次甲基四胺，不断搅拌至各组分混合均匀；按照沥青和树脂总重量：锡粉：分散溶剂的重量为1:0.09：0.27的比例称取1.35Kg平均粒径为50nm的锡粉和4.05公斤的二甲苯溶液，将锡粉加入到二甲苯溶液后，通过超声波装置进行分散，分散均有后，加入已混合均匀的沥青、树脂、固化剂的混合液体中，搅拌150min后通过离心雾化装置喷洒冷却，并通过旋风分离器收集平均粒径介于5～30μm之间的粉体，然后在氮气保护下加热至850℃，保温3小时，然后冷却至室温，最终得到高容量锡碳电池负极材料。
检验实施例2锂离子电池负极材料的性能，采用实施例1相同的检测方法进行检测，该电机材料的首次放电容量达416mAh/g，100次循环后的容量仍有379mAh/g，保持率为91.1％。
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。

Claims (9)

  1. 一种高容量锡碳负极材料的制备方法，其制备步骤如下：
    (1)将软化点在100℃～300℃之间的沥青和软化点在50℃～150℃之间的树脂按1：1.5～4的重量比加入到具有加热和搅拌装置的捏合釜中，以10～40℃/min的速率加热升温至沥青和树脂均熔化成液体；
    (2)然后加入占树脂量2％～5％的固化剂，在惰性气体保护下，不断搅拌至各种组分混合均匀；
    (3)按照树脂和沥青总重量：锡粉：分散溶剂的重量为1:0.05～0.15：0.2～0.6的比例称取锡粉和分散溶剂，将锡粉加入到分散溶剂中，并超声分散均匀后加入到步骤2中的混合液体中，搅拌至各组分混合均匀；
    (4)将步骤(3)中混合均匀的液体通过雾化装置雾化冷却，再对雾化所得的粉体进行收集并进行分级处理，得到平均粒径介于于5～30μm之间的粉体，此时树脂已完成固化；
    (5)将步骤(4)中所得到的粉体在惰性气体的保护下，以1～10℃/min的速度升温至700～900℃，再保温1～5h，自然降温，冷却后即得到高容量锡碳负极材料。
  2. 一种高容量锡碳负极材料的制备方法，其特征是：步骤(1)中所述的沥青包括煤沥青、石油沥青、改质沥青、中间相沥青、由沥青改质而得到的缩合多环多核芳香烃中的一种或一种以上的混合物，软化点在100℃以上。
  3. 一种高容量锡碳负极材料的制备方法，其特征是：步骤(1)中所述的树脂为热塑性树脂，包括呋喃树脂、脲醛树脂、嘧胺树脂、酚醛树脂、环氧树脂和聚甲醛丙烯酸甲酯树脂中的一种或一种以上的混合物。
  4. 一种高容量锡碳负极材料的制备方法，其特征是：步骤(1)中所述的搅拌的时间为80～130min，加热的最终温度比组分中沥青和树脂的最高软化点高30～40℃。
  5. 一种高容量锡碳负极材料的制备方法，其特征是：步骤(2)中所述的固化剂为六次甲基四胺、二乙胺基丙胺、三甲基六亚甲基二胺、二已基三胺、具有固化作用的热固性树脂中的一种或一种以上的混合物。
  6. 一种高容量锡碳负极材料的制备方法，其特征是：步骤(3)中所述的锡粉的平均粒径≤100nm。
  7. 一种高容量锡碳负极材料的制备方法，其特征是：步骤(3)中所述的分散溶剂为乙醇、异丙醇、二硫化碳、甲苯、二甲苯或者带有分散介质的蒸馏水中的一种。
  8. 一种高容量锡碳负极材料的制备方法，其特征是：步骤(4)中雾化采用的是利用超声雾化、离心雾化、高压雾化原理工作的雾化装置中的一种。
  9. 一种高容量锡碳负极材料的制备方法，其特征是：步骤(4)中分级处理采用的是对粉体进行旋风分离、过筛处理中的一种或两者的结合。
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