WO2017024897A1 - 一种改性锂电池负极材料的制备方法 - Google Patents

一种改性锂电池负极材料的制备方法 Download PDF

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WO2017024897A1
WO2017024897A1 PCT/CN2016/086701 CN2016086701W WO2017024897A1 WO 2017024897 A1 WO2017024897 A1 WO 2017024897A1 CN 2016086701 W CN2016086701 W CN 2016086701W WO 2017024897 A1 WO2017024897 A1 WO 2017024897A1
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powder
graphite
tin
phenolic resin
modified lithium
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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 a preparation method of a lithium ion battery anode material, in particular to a preparation method of a modified lithium battery anode material.
  • 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.
  • 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.
  • 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.
  • tin or its alloys have a great improvement in both capacity and cycle performance.
  • the particles of the alloy material reach the nanometer level, the volume expansion during charging and discharging is greatly reduced, and the performance is also greatly reduced. It will be improved, but the nanomaterials have a large surface energy and are prone to agglomeration, which in turn will reduce the charge and discharge efficiency and accelerate the attenuation of the capacity, thereby offsetting the advantages of the nanoparticles.
  • Another research trend to improve the performance of tin anodes is to prepare composites or alloys of tin and other materials. Among them, tin/carbon composites prepared by combining the stability of carbon materials with the high specific capacity of tin have shown great application. prospect.
  • the technical problem to be solved by the present invention is to provide a method for preparing a negative electrode material for a modified lithium battery to solve the disadvantages in the above background art.
  • a preparation method of a negative electrode material for a modified lithium battery comprising the following steps: (1) graphite, phenolic resin, nano tin powder according to 100:5-20:5-10, solid content is 20% ⁇ 40% ratio, first weigh a certain amount of nano tin powder into an alcohol solvent, and ultrasonically disperse, then add phenolic resin and graphite separately, and add hexamethylenetetramine with a resin content of 3% to 5%.
  • the resin curing agent is continuously stirred and mixed into a uniform slurry; (2) the uniformly mixed slurry is spray-dried to obtain a graphite powder having a surface coated with a mixture of nano tin and a phenolic resin; (3) the obtained powder is further obtained.
  • the body and the asphalt powder are uniformly mixed in a ratio of 100:5 to 20; (4) the obtained powder is heated to a temperature of 800 to 1000 ° C at a rate of 1 to 5 ° C/min under the protection of an inert gas. Insulation for 1 to 5 hours, natural cooling, and after cooling, the high-capacity modified graphite anode material is obtained.
  • the graphite is natural graphite or artificial graphite, and has an average particle diameter of 5 to 30 ⁇ m, a tap density of ⁇ 0.75 g/cm 3 , and a specific surface area of ⁇ 6 m 2 /g.
  • the particle size of the tin powder is not more than 100 nm.
  • the inlet temperature of the spray-dried hot air is from 150 ° C to 200 ° C, and the outlet temperature is from 40 ° C to 70 ° C.
  • the asphalt powder includes a powder prepared from one or more of a mixture 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 from 100 to 280 ° C and the average particle diameter is from 2 to 5 ⁇ m.
  • phenolic resin, nano tin powder according to 100:10:5, solid content of 30% weigh 100g of nano tin powder into 5366g of alcohol solvent, and ultrasonic dispersion, then add 200g of phenolic resin And 2000g of natural graphite, adding 6g of hexamethylenetetramine with a resin content of 3%, stirring constantly, mixing into a uniform slurry; then spraying the slurry to obtain graphite powder with a mixture of nano tin and phenolic resin on the surface
  • the temperature is raised to 1000 ° C at a rate of 5 ° C / min under the protection of an inert gas, and then kept for 3 h, naturally cooled, and sieved after cooling. That is, the modified negative electrode material of the present invention is obtained.
  • phenolic resin, nano tin powder according to 100:15:5, solid content of 30% weigh 100g of nano tin powder into 5600g of alcohol solvent, and ultrasonic dispersion, then add 300g of phenolic resin And 2000g of natural graphite, adding 9g of hexamethylenetetramine with a resin content of 3%, stirring constantly, mixing into a uniform slurry; then spraying the slurry to obtain graphite powder with a mixture of nano tin and phenolic resin on the surface
  • the temperature is raised to 900 ° C at a rate of 3 ° C / min under the protection of an inert gas, and then kept for 4 h, naturally cooled, and sieved after cooling. That is, the modified negative electrode material of the present invention is obtained.
  • phenolic resin, nano tin powder according to 100:15:10, solid content of 30% weigh 200g of nano tin powder into 5833g of alcohol solvent, and ultrasonic dispersion, then add 300g of phenolic resin And 2000g of natural graphite, adding 9g of hexamethylenetetramine with a resin content of 3%, stirring constantly, mixing into a uniform slurry; then spraying the slurry to obtain graphite powder with a mixture of nano tin and phenolic resin on the surface Body, then mix the powder and asphalt powder in a ratio of 100:5, and then heat up to 950 ° C at 4 ° C / min under the protection of inert gas, then keep warm for 2.5 h, naturally cool, after cooling
  • the modified negative electrode material of the present invention is obtained by sieving.
  • the solid content is 30%
  • 200g of phenolic resin and 2000g of natural graphite are placed in 5113g of alcohol solvent, and 6g of hexamethylenetetramine with a resin content of 3% is continuously added.
  • Stirring mixing into a uniform slurry; then spraying the slurry to obtain a graphite powder coated with a phenolic resin mixture on the surface, and then mixing the powder and the asphalt powder in a ratio of 100:5, and then in an inert gas
  • the temperature is raised to 1000 ° C at 5 ° C / min, and then kept for 3 h, and the temperature is naturally lowered.
  • the high-capacity modified graphite anode material is obtained by sieving.
  • Table 1 compares the performance of negative electrode materials in different examples and comparative examples.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

一种改性锂电池负极材料的制备方法，原料按照重量份比例，包括以下步骤：(1)将石墨、酚醛树脂、纳米锡粉加入树脂量3％～5％的六次甲基四胺，混合成均匀浆体；(2)将混合均匀的浆体通过喷雾干燥，得到表面包裹有纳米锡和酚醛树脂混合物的石墨粉体；(3)将所得到的粉体与沥青粉体混合均匀；(4)将所得到的粉体通过高温处理。通过选用纳米锡粉，避免了锡粉因粒径较大而在充放电时产生的体积效应，保证了材料的在充放电过程中的稳定性。

Description

一种改性锂电池负极材料的制备方法 技术领域
本发明涉及一种锂离子电池负极材料的制备方法，具体为一种改性锂电池负极材料的制备方法。
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。
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。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。
研究表明，小粒径的锡或其合金无论在容量上还是在循环性能上都有很大的提高，当合金材料的颗粒达到纳米级时，充放电过程中的体积膨胀会大大减轻，性能也会有所提高，但是纳米材料具有较大的表面能，容易发生团聚，反而会使充放电效率降低并加快容量的衰减，从而抵消了纳米颗粒的优点。另外一种改善锡负极性能的研究趋势就是制备锡与其它材料的复合材料或合金，其中，结合碳材料的稳定性和锡的高比容量特性而制备的锡/碳复合材料显示了巨大的应用前景。
发明内容
本发明所解决的技术问题在于提供一种改性锂电池负极材料的制备方法，以解决上述背景技术中的缺点。
一种改性锂电池负极材料的制备方法，原料按照重量份比例，包括以下步骤：(1)将石墨、酚醛树脂、纳米锡粉按照100：5～20：5～10，固含量为20％～40％的比例，首先称取一定量的纳米锡粉放入酒精溶剂中，并超声分散，然后分别加入酚醛树脂和石墨，同时加入树脂量3％～5％的六次甲基四胺作为树脂固化剂，不断搅拌，混合成均匀浆体；(2)将混合均匀的浆体通过喷雾干燥，得到表面包裹有纳米锡和酚醛树脂混合物的石墨粉体；(3)再将所得到的粉体与沥青粉体按照100：5～20的比例混合均匀；(4)再将所得到的粉体在惰性气体的保护下，以1～5℃/min的速度升温至800～1000℃，再保温1～5h，自然降温，冷却后过筛即得到高容量改性石墨负极材料。
进一步，石墨为天然石墨或人造石墨，平均粒径为5～30μm、振实密度≥0.75g/cm3、比表面积≤6m2/g。
进一步，锡粉的粒径不大于100纳米。
进一步，喷雾干燥的热空气的进口温度为150℃～200℃，出口温度为40℃～70℃。
进一步，沥青粉体包括由煤沥青、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所制备的粉体，软化点在100--280℃，平均粒径为2～5μm。
有益效果
(1)通过选用纳米锡粉，避免了锡粉因粒径较大而在充放电时产生的体积效应，保证了材料的在充放电过程中的稳定性，同时和石墨进行复合包覆处理，解决了单一石墨负极材料容量偏低等缺点；
(2)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，这些空隙可以起到缓冲锡粉的体积效应，保证材料体系的稳定；
(3)通过最后用沥青对材料进行二次包覆，降低了材料的比表面积，提高了材料的首次充放电效率；
(4)通过在前面步骤添加树脂固化剂——六次甲基四胺，让树脂在喷雾干燥步骤 中受热固化，因此不会因为第二次受热而熔化，避免了后期又因添加沥青而导致高温烧结后结块严重的问题。
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，下面结合具体实施例，进一步阐述本发明。
实施例1
按照石墨、酚醛树脂、纳米锡粉按照100：10：5，固含量为30％的比例，称取100g的纳米锡粉放入5366g的酒精溶剂中，并超声分散，然后分别加入200g的酚醛树脂和2000g天然石墨，同时加入树脂量3％的六次甲基四胺6g，不断搅拌，混合成均匀浆体；再将浆体进行喷雾干燥，得到表面包裹有纳米锡和酚醛树脂混合物的石墨粉体，再将粉体与沥青粉体按照100：5的比例混合均匀后，在惰性气体的保护下，以5℃/min的速度升温至1000℃，再保温3h，自然降温，冷却后过筛即得到本发明改性负极材料。
实施例2
按照石墨、酚醛树脂、纳米锡粉按照100：15：5，固含量为30％的比例，称取100g的纳米锡粉放入5600g的酒精溶剂中，并超声分散，然后分别加入300g的酚醛树脂和2000g天然石墨，同时加入树脂量3％的六次甲基四胺9g，不断搅拌，混合成均匀浆体；再将浆体进行喷雾干燥，得到表面包裹有纳米锡和酚醛树脂混合物的石墨粉体，再将粉体与沥青粉体按照100：5的比例混合均匀后，在惰性气体的保护下，以3℃/min的速度升温至900℃，再保温4h，自然降温，冷却后过筛即得到本发明改性负极材料。
实施例3
按照石墨、酚醛树脂、纳米锡粉按照100：15：10，固含量为30％的比例，称取200g的纳米锡粉放入5833g的酒精溶剂中，并超声分散，然后分别加入300g的酚醛树脂和2000g天然石墨，同时加入树脂量3％的六次甲基四胺9g，不断搅拌，混合成均匀浆体；再将浆体进行喷雾干燥，得到表面包裹有纳米锡和酚醛树脂混合物的石墨粉体，再将粉体与沥青粉体按照100：5的比例混合均匀后，在惰性气体的保护下，以4℃/min的速度升温至950℃，再保温2.5h，自然降温，冷却后过筛即得到本发明改性负极材料。
对比例1
按照石墨、酚醛树脂按照100：10，固含量为30％的比例，200g的酚醛树脂和2000g天然石墨放入5113g的酒精溶剂中，同时加入树脂量3％的六次甲基四胺6g，不断搅拌，混合成均匀浆体；再将浆体进行喷雾干燥，得到表面包裹有酚醛树脂混合物的石墨粉体，再将粉体与沥青粉体按照100：5的比例混合均匀后，在惰性气体的保护下，以5℃/min的速度升温至1000℃，再保温3h，自然降温，冷却后过筛即得到高容量改性石墨负极材料。
对比例2
未经任何处理的天然球形石墨直接进行电性能测试。
电化学性能测试
为检验本发明方法制备的锂离子改性负极材料的性能，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1。
表1为不同实施例和比较例中负极材料的性能比较
Figure PCTCN2016086701-appb-000001
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。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。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (5)

  1. 一种改性锂电池负极材料的制备方法，原料按照重量份比例，其特征在于，包括以下步骤：
    (1)将石墨、酚醛树脂、纳米锡粉按照100：5～20：5～10，固含量为20％～40％的比例，首先称取一定量的纳米锡粉放入酒精溶剂中，并超声分散，然后分别加入酚醛树脂和石墨，同时加入树脂量3％～5％的六次甲基四胺作为树脂固化剂，不断搅拌，混合成均匀浆体；
    (2)将混合均匀的浆体通过喷雾干燥，得到表面包裹有纳米锡和酚醛树脂混合物的石墨粉体；
    (3)再将所得到的粉体与沥青粉体按照100：5～20的比例混合均匀；
    (4)再将所得到的粉体在惰性气体的保护下，以1～5℃/min的速度升温至800～1000℃，再保温1～5h，自然降温，冷却后过筛即可。
  2. 根据权利要求1所述的一种改性锂电池负极材料的制备方法，其特征在于，石墨为天然石墨或人造石墨，平均粒径为5～30μm、振实密度≥0.75g/cm3、比表面积≤6.0m2/g。
  3. 根据权利要求1所述的一种改性锂电池负极材料的制备方法，其特征在于，锡粉的粒径不大于100纳米。
  4. 根据权利要求1所述的一种改性锂电池负极材料的制备方法，其特征在于，喷雾干燥的热空气的进口温度为150℃～200℃，出口温度为40℃～70℃。
  5. 根据权利要求1所述的一种改性锂电池负极材料的制备方法，其特征在于，沥青粉体包括由煤沥青、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所制备的粉体，软化点在100--280℃，平均粒径为2～5μm。
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