CN103050668A - Method for preparing Si/C composite cathode material for lithium ion battery - Google Patents
Method for preparing Si/C composite cathode material for lithium ion battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 13
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- 239000010406 cathode material Substances 0.000 title 1
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种锂离子电池用硅碳(Si/C)复合负极材料的制备方法,将石墨和金属盐类添加剂均匀分散在浓硫酸溶液中;通过氧化反应制备微氧化石墨;将获得的微氧化石墨与硅源分散在溶有碳源和有机添加剂的溶液中,超声分散,搅拌混匀后得到悬浮液,将悬浮液蒸干后,在600~1000℃下进行热处理,即得;该方法简单易行,实用化程度高,制备的复合材料具有形貌好、振实密度高、容量高、循环性能及倍率性能好等优点。The invention discloses a method for preparing a silicon-carbon (Si/C) composite negative electrode material for a lithium-ion battery. Graphite and metal salt additives are uniformly dispersed in concentrated sulfuric acid solution; micro-oxidized graphite is prepared through an oxidation reaction; the obtained Micro-oxidized graphite and silicon source are dispersed in a solution containing carbon source and organic additives, ultrasonically dispersed, stirred and mixed to obtain a suspension, evaporated to dryness, and heat-treated at 600-1000°C to obtain the product; The method is simple and easy to implement, and has a high degree of practicality. The prepared composite material has the advantages of good shape, high tap density, high capacity, good cycle performance and rate performance, and the like.
Description
技术领域technical field
本发明属于锂离子电池材料及其制备方法领域,涉及一种锂离子电池硅碳复合负极材料及其制备方法。The invention belongs to the field of lithium-ion battery materials and preparation methods thereof, and relates to a lithium-ion battery silicon-carbon composite negative electrode material and a preparation method thereof.
背景技术Background technique
锂离子电池因其自身固有的优势,如能量密度大、工作电压高、使用寿命长、便于携带等,广泛应用于便携式电子设备和电动汽车中。商业化的锂离子电池负极材料石墨因其容量限制(372mAh·g-1)逐渐不能满足高能量密度电池的需求。因此开发替代石墨的新型负极材料备受关注。Lithium-ion batteries are widely used in portable electronic devices and electric vehicles due to their inherent advantages, such as high energy density, high operating voltage, long service life, and portability. Due to its limited capacity (372mAh·g -1 ), commercial lithium-ion battery anode material graphite cannot meet the needs of high energy density batteries. Therefore, the development of new anode materials to replace graphite has attracted much attention.
硅基材料因具有最高比容量(4200mAh·g-1)、低脱嵌锂电位(0.02~0.6V vs.Li+/Li)而被认为是最优希望提高改善锂离子电池负极材料性能的材料之一。然而硅负极在脱嵌锂过程中严重的体积膨胀和收缩(>300%),造成材料结构的破坏和机械粉碎,从而限制了其商业化应用。为改善这些问题,目前主要通过将硅纳米化、硅与金属合金化、制备硅薄膜已将将硅与活性或者非活性基质复合等方式来改善其性能,其中硅碳复合材料具有更好的应用前景。硅碳复合材料中,碳是离子与电子的混合导体,碳材料构成的“缓冲骨架”可以补偿硅颗粒的体积膨胀,在充放电过程中体积变化小,可以维持电极材料的结构稳定性和良好的导电性,从而使得硅基材料的循环性能得到改善。此外,碳材料与硅的嵌锂电位相近,材料容量损失相对较小。Silicon-based materials are considered to be the best materials for improving the performance of lithium-ion battery anode materials due to their highest specific capacity (4200mAh·g -1 ) and low lithium-extraction potential (0.02~0.6V vs. Li + /Li) one. However, the severe volume expansion and contraction (>300%) of the silicon anode during the process of lithium intercalation and deintercalation results in the destruction of the material structure and mechanical crushing, thus limiting its commercial application. In order to improve these problems, at present, silicon nanometerization, silicon and metal alloying, preparation of silicon thin films, and compounding of silicon with active or inactive substrates are mainly used to improve its performance. Among them, silicon-carbon composite materials have better applications. prospect. In silicon-carbon composite materials, carbon is a mixed conductor of ions and electrons. The "buffer skeleton" composed of carbon materials can compensate the volume expansion of silicon particles, and the volume change is small during charging and discharging, which can maintain the structural stability and good performance of electrode materials. The electrical conductivity of silicon-based materials is improved. In addition, the lithium intercalation potential of carbon materials is similar to that of silicon, and the material capacity loss is relatively small.
发明内容Contents of the invention
本发明的目的是在于提供一种简单快速制备形貌好、振实密度高、容量高、循环性及倍率性能好的锂离子电池硅碳复合负极材料的方法。The purpose of the present invention is to provide a simple and rapid method for preparing a silicon-carbon composite negative electrode material for a lithium-ion battery with good appearance, high tap density, high capacity, good cycleability and rate performance.
本发明提供了一种锂离子电池Si/C复合负极材料的制备方法,该方法是将石墨和金属盐类添加剂均匀分散在浓硫酸溶液中;先在不高于2℃下加入氧化剂反应,再在32~38℃中反应,反应完全后用去离子水稀释反应液,或者先在不大于2℃下加入氧化剂反应,再在32~38℃中反应,接着用去离子水稀释反应液,再在92~98℃下继续反应,反应完成后继续用去离子水稀释反应液并添加双氧水;将最后得到的稀释过的反应液固液分离,分离得到的固体用稀盐酸和去离子水洗至pH值为3~4,干燥后获得微氧化石墨;将获得的微氧化石墨与硅源分散在溶有碳源和有机添加剂的溶液中,超声分散,搅拌混匀后得到悬浮液,将悬浮液蒸干后,在600~1000℃下进行热处理,即得;其中硅源:石墨:碳源热解后所得热解碳的质量比为x:y:(1-x-y),其中0<x<1,0<y<1;硅源的添加量占Si/C复合材料的5~30wt.%,碳源的添加量以热处理后所得热解碳计为Si/C复合材料的10~50wt.%。The invention provides a method for preparing a Si/C composite negative electrode material for a lithium ion battery. The method is to uniformly disperse graphite and metal salt additives in a concentrated sulfuric acid solution; React at 32~38°C, dilute the reaction solution with deionized water after the reaction is complete, or add an oxidant to react at no more than 2°C, then react at 32~38°C, then dilute the reaction solution with deionized water, and then Continue the reaction at 92~98°C. After the reaction is completed, continue to dilute the reaction solution with deionized water and add hydrogen peroxide; separate the solid and liquid of the final diluted reaction solution, and wash the separated solid with dilute hydrochloric acid and deionized water to pH The value is 3~4, and micro-oxidized graphite is obtained after drying; the obtained micro-oxidized graphite and silicon source are dispersed in a solution containing carbon source and organic additives, ultrasonically dispersed, stirred and mixed to obtain a suspension, and the suspension is evaporated After drying, conduct heat treatment at 600~1000°C to obtain it; wherein the mass ratio of silicon source:graphite:carbon source pyrolysis is x:y:(1-x-y), where 0<x<1 , 0<y<1; the added amount of silicon source accounts for 5~30wt.% of the Si/C composite material, and the added amount of carbon source is calculated as 10~50wt.% of the Si/C composite material based on the pyrolytic carbon obtained after heat treatment .
上述制备方法中微氧化石墨的制备:先在不高于2℃下加入氧化剂反应0.3~0.8h,再在32~38℃下反应1~3h;或者是先在不高于2℃下加入氧化剂反应0.3~0.8h,再在32~38℃下反应1~3h,再在92~98℃下继续反应1~3h;根据需要将石墨氧化的程度,来选择氧化反应的方式。The preparation of micro-oxidized graphite in the above preparation method: first add an oxidant to react at no higher than 2°C for 0.3~0.8h, and then react at 32~38°C for 1~3h; or first add an oxidant at a temperature not higher than 2°C React for 0.3~0.8h, then react at 32~38°C for 1~3h, and then continue to react at 92~98°C for 1~3h; choose the way of oxidation reaction according to the degree of oxidation of graphite.
所述双氧水用量为石墨质量的0.5~10倍;去离子水用量为浓硫酸体积的1~5倍。The amount of hydrogen peroxide used is 0.5 to 10 times the mass of graphite; the amount of deionized water used is 1 to 5 times the volume of concentrated sulfuric acid.
所述的石墨包括:人工石墨、天然石墨或石墨化中间相碳微球中的一种或几种。The graphite includes: one or more of artificial graphite, natural graphite or graphitized mesocarbon microspheres.
所述的硅源包括:纳米硅粉、氧化硅粉、碳包覆纳米硅粉、碳包覆氧化硅粉中的一种或几种,其中氧化硅粉为SiOx,O<x≤2。The silicon source includes: one or more of nano-silicon powder, silicon oxide powder, carbon-coated nano-silicon powder, and carbon-coated silicon oxide powder, wherein the silicon oxide powder is SiO x , where O<x≤2.
所述的碳源包括:石墨烯、酚醛树脂、脲醛树脂、环氧树脂、聚乙烯、过氯乙烯、聚乙烯醇、沥青、葡萄糖、柠檬酸或蔗糖中的一种或几种。The carbon source includes: one or more of graphene, phenolic resin, urea-formaldehyde resin, epoxy resin, polyethylene, perchlorethylene, polyvinyl alcohol, pitch, glucose, citric acid or sucrose.
所述的氧化剂为双氧水、重铬酸钾或高锰酸钾中的一种或几种;其中双氧水的用量为石墨质量的0.5~20倍,重铬酸钾的用量为石墨质量的1.5~2.5倍,高锰酸钾的用量为石墨质量的0.5~4倍。The oxidant is one or more of hydrogen peroxide, potassium dichromate or potassium permanganate; wherein the amount of hydrogen peroxide is 0.5 to 20 times the mass of graphite, and the amount of potassium dichromate is 1.5 to 2.5 times the mass of graphite. times, the dosage of potassium permanganate is 0.5~4 times of graphite mass.
所述热处理是在氩气或者氮气环境中处理1~6h。The heat treatment is performed in an argon or nitrogen environment for 1-6 hours.
所述溶有碳源和有机添加剂的溶液中的溶剂为去离子水、四氢呋喃、丙酮、吡咯、乙酸乙酯或无水乙醇中的一种或几种。The solvent in the solution containing the carbon source and the organic additive is one or more of deionized water, tetrahydrofuran, acetone, pyrrole, ethyl acetate or absolute ethanol.
所述的固液分离为将稀释后的溶液静置后过滤分离或者离心分离;悬浮液蒸干方式包括蒸发固化、真空干燥或喷雾干燥中的一种或几种。The solid-liquid separation refers to filtering and centrifuging the diluted solution after standing; the method of evaporating the suspension to dryness includes one or more of evaporative solidification, vacuum drying or spray drying.
所述的金属盐添加剂为硝酸钠或硝酸钾中的一种或几种。The metal salt additive is one or more of sodium nitrate or potassium nitrate.
所述的有机添加剂包括:聚丙烯酰胺、聚乙二醇、丙二醇、聚醋酸乙烯脂、N-N二甲基乙酰胺、海藻酸钠、十二烷基苯磺酸钠、十六烷基溴化胺或无水乙醇中的一种或几种。The organic additives include: polyacrylamide, polyethylene glycol, propylene glycol, polyvinyl acetate, N-N dimethylacetamide, sodium alginate, sodium dodecylbenzenesulfonate, hexadecylamine bromide Or one or more of absolute ethanol.
所述的蒸发固化的温度为70~120℃;喷雾干燥温度为170~200℃;真空干燥的温度为60~90℃。The evaporation solidification temperature is 70-120°C; the spray drying temperature is 170-200°C; the vacuum drying temperature is 60-90°C.
本发明技术特征:采用液相处理制备微氧化石墨,具有良好的形貌,所得微氧化石墨为多孔结构,为与硅源的结合建立了良好的基础;在此基础上制备Si/C负极材料,制备的Si/C复合材料具有良好的形貌,硅源能够更好的与石墨结合,并在其表面形成均匀的碳包覆层;这种结构有利于材料的强度、韧性的增加以及振实密度的提高;同时本方法具备对原料适应性强、操作简单等优点。Technical features of the present invention: use liquid phase treatment to prepare micro-oxidized graphite, which has a good shape, and the obtained micro-oxidized graphite has a porous structure, which establishes a good foundation for the combination with silicon source; on this basis, Si/C negative electrode material is prepared , the prepared Si/C composite material has a good morphology, the silicon source can be better combined with graphite, and a uniform carbon coating layer is formed on the surface; this structure is conducive to the increase of the strength, toughness and vibration of the material. Solid density is improved; at the same time, the method has the advantages of strong adaptability to raw materials, simple operation and the like.
本发明具有的有益效果是:The beneficial effects that the present invention has are:
本发明的微氧化石墨复合硅碳复合负极材料,具有以下优点:通过对石墨进行微氧化处理,改变其形貌及表面活性,为硅的嵌入预留孔隙,为与小颗粒硅源的结合建立基础。在此基础上,部分硅源嵌入到微氧化石墨孔隙中,同时与微氧化石墨更好的结合,碳源通过热解在复合材料表面形成密实均匀的包覆层。在热解过程中,碳源不会呈纯液体状态,不会填充硅与微氧化石墨复合剩余的所有孔隙中,形成了良好的“缓冲骨架”,同时热解碳材料的存在增强了材料的导电性能。因此,制备的复合材料能够明显提高Si/C复合材料的强度、韧性增强了材料的结构稳定性,在一定程度上缓解了硅基负极材料电极结构在充放电过程中的崩塌程度,同时改善Si/C复合材料的导电性,从而增强了材料的循环稳定性和倍率性能。The micro-oxidized graphite composite silicon-carbon composite negative electrode material of the present invention has the following advantages: through micro-oxidation treatment of graphite, its morphology and surface activity are changed, pores are reserved for the embedding of silicon, and the combination with small particle silicon sources is established. Base. On this basis, part of the silicon source is embedded in the pores of the micro-graphite oxide, and at the same time, it is better combined with the micro-graphite oxide. The carbon source forms a dense and uniform coating layer on the surface of the composite material through pyrolysis. During the pyrolysis process, the carbon source will not be in a pure liquid state, and will not fill all the remaining pores in the composite of silicon and micro-graphite oxide, forming a good "buffer skeleton". Electrical conductivity. Therefore, the prepared composite material can significantly improve the strength and toughness of the Si/C composite material, enhance the structural stability of the material, alleviate the collapse of the electrode structure of the silicon-based negative electrode material during the charge and discharge process to a certain extent, and improve the Si /C composites are electrically conductive, thereby enhancing the cycle stability and rate performance of the material.
由液相氧化所得微氧化石墨为多孔隙结构,因此为与硅的复合提供了更好的复合孔隙,在碳源包覆基础上,获得球形或不规则颗粒,提高了材料的振实密度,从而能量密度也得到一定程度的提升。The micro-oxidized graphite obtained by liquid phase oxidation has a porous structure, so it provides better composite pores for the composite with silicon. On the basis of carbon source coating, spherical or irregular particles are obtained, which improves the tap density of the material. As a result, the energy density is also improved to a certain extent.
在Si/C复合材料中,硅源:石墨:热解碳质量比=x:y:(1-x-y),其中硅源容量较高(如纳米硅粉为4200mAh·g-1),是决定复合材料容量的关键活性材料,因此可以通过调整硅源组分及在复合材料中所占比例,得到高容量Si/C复合负极材料。In Si/C composite materials, the mass ratio of silicon source:graphite:pyrolytic carbon=x:y:(1-xy), in which the capacity of silicon source is higher (such as nano silicon powder is 4200mAh·g -1 ), is the decision The key active material of the capacity of the composite material, therefore, the high-capacity Si/C composite negative electrode material can be obtained by adjusting the silicon source component and its proportion in the composite material.
附图说明Description of drawings
【图1】为天然石墨在液相微氧化前后的SEM图,a为天然石墨的SEM图,b为微氧化天然石墨的SEM图。[Figure 1] is the SEM image of natural graphite before and after liquid phase micro-oxidation, a is the SEM image of natural graphite, and b is the SEM image of micro-oxidized natural graphite.
【图2】为本发明实施例2的SEM图:a为实施例2中纳米硅粉的SEM图,b为实施例2中碳包覆后纳米硅粉的SEM图;c为实施例2中制备Si/C复合负极材料的SEM图。[Fig. 2] is the SEM figure of Example 2 of the present invention: a is the SEM figure of nano-silicon powder in Example 2, b is the SEM figure of nano-silicon powder after carbon coating in Example 2; c is the SEM figure of Example 2 The SEM image of the prepared Si/C composite anode material.
具体实施方式Detailed ways
下面结合附图和具体实施方式对本发明作进一步说明。以下实施实例旨在说明本发明而不是对本发明的进一步限定。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. The following implementation examples are intended to illustrate the present invention rather than to further limit the present invention.
实施例1Example 1
量取浓H2SO4溶液120mL,向该溶液中加入适量硝酸钾以及10g天然石墨后,放置于0℃冰浴中,磁力搅拌0.5h;称取一定量5~20g的高锰酸钾缓慢的加入到上述料液中,于38℃中温反应1.5h后,缓慢加入大量的去离子水稀释至1L左右,并控制料液温度在100℃以下;静置后过滤,用大量无水乙醇以及去离子水洗至pH值为3~4,烘干备用,氧化前后石墨形貌如图1所示。按复合材料设计容量称取1g纳米硅粉、2g微氧化石墨、以及5g葡萄糖溶于适量去离子水中,以0.15g十六烷基溴化胺作为分散剂,超声1h,搅拌均匀后进行真空干燥,所得固体转入程序控温炉中在氮气或者氩气气氛中于800℃进行高温处理1~6h后得Si/C复合负极材料。Measure 120mL of concentrated H2SO4 solution, add an appropriate amount of potassium nitrate and 10g of natural graphite to the solution, place it in an ice bath at 0°C, and stir it magnetically for 0.5h; weigh a certain amount of 5~20g of potassium permanganate and slowly Add it to the above-mentioned feed liquid, react at a medium temperature of 38°C for 1.5h, slowly add a large amount of deionized water to dilute to about 1L, and control the temperature of the feed liquid below 100°C; filter after standing, and use a large amount of absolute ethanol and Wash with deionized water until the pH value is 3~4, and dry for later use. The morphology of graphite before and after oxidation is shown in Figure 1. Weigh 1g of nano-silica powder, 2g of micro-oxidized graphite, and 5g of glucose according to the design capacity of the composite material, dissolve them in an appropriate amount of deionized water, use 0.15g of hexadecyl ammonium bromide as a dispersant, ultrasonicate for 1h, stir evenly, and then carry out vacuum drying , the obtained solid is transferred to a temperature-programmed furnace and subjected to a high-temperature treatment at 800° C. for 1 to 6 hours in a nitrogen or argon atmosphere to obtain a Si/C composite negative electrode material.
实施例2Example 2
量取200mL浓H2SO4溶液,向该溶液中加入适量硝酸钾以及5g天然石墨粉后,放置于0℃冰浴中,磁力搅拌0.5h;称取5~20g高锰酸钾缓慢的加入到上述料液中,控制反应温度在2℃以下,于35℃中温反应2h后,缓慢加入大量的去离子水稀释至0.6L左右,并控制料液温度在100℃以下;然后在95℃下高温反应2h后加入适量双氧水以及400~800mL去离子水,离心分离,并用大量无水乙醇以及去离子水洗至pH值为3~4,冷冻干燥后备用。在纳米硅表面包覆10%葡萄糖热解碳,包覆前后形貌如图2(a)及图2(b)所示,按复合材料设计容量称取1g纳米硅粉、2g微氧化石墨、以及1.67g葡萄糖溶于适量去离子水中,0.15g十二烷基苯磺酸钠作为分散剂,超声1h,搅拌均匀后进行喷雾干燥,所得固体转入程序控温炉中在氮气或者氩气气氛中于800℃进行高温处1~6h后得Si/C复合负极材料,如图2(c)所示。Measure 200mL of concentrated H 2 SO 4 solution, add appropriate amount of potassium nitrate and 5g of natural graphite powder to the solution, place it in an ice bath at 0°C, and stir magnetically for 0.5h; weigh 5~20g of potassium permanganate and slowly add Into the above feed liquid, control the reaction temperature below 2°C, react at a medium temperature at 35°C for 2 hours, slowly add a large amount of deionized water to dilute to about 0.6L, and control the temperature of the feed liquid below 100°C; then at 95°C After high-temperature reaction for 2 hours, add appropriate amount of hydrogen peroxide and 400-800 mL of deionized water, centrifuge, wash with a large amount of absolute ethanol and deionized water until the pH value is 3-4, freeze-dry and set aside. 10% glucose pyrolytic carbon was coated on the surface of nano-silicon, and the morphology before and after coating was shown in Figure 2(a) and Figure 2(b). Weighed 1g nano-silicon powder, 2g micro-graphite oxide, And 1.67g of glucose was dissolved in an appropriate amount of deionized water, 0.15g of sodium dodecylbenzenesulfonate was used as a dispersant, ultrasonicated for 1h, stirred evenly, and then spray-dried, and the obtained solid was transferred to a temperature-programmed furnace in a nitrogen or argon atmosphere The Si/C composite anode material was obtained after a high temperature treatment at 800 °C for 1~6 h, as shown in Figure 2(c).
实施例3Example 3
量取浓H2SO4溶液,向该溶液中加入适量硝酸钠以及10g天然石墨粉后,放置于0℃冰浴中,磁力搅拌0.5h;称取15~25g重铬酸钾缓慢的加入到上述料液中,于38℃中温反应1.5h后,缓慢加入大量的去离子水稀释至1L左右,并控制料液温度在100℃以下;静置后过滤,用大量无水乙醇以及去离子水洗至pH值为3~4,烘干备用。按复合材料设计容量称取纳米硅粉、微氧化石墨、以及酚醛树脂溶于适量无水乙醇中,超声1h,搅拌2h后在80℃蒸干,所得固体干燥后转入程序控温炉中在氮气或者氩气气氛中于800℃进行高温处1~6h后得Si/C复合负极材料。Measure the concentrated H 2 SO 4 solution, add appropriate amount of sodium nitrate and 10g of natural graphite powder to the solution, place it in an ice bath at 0°C, and stir it magnetically for 0.5h; weigh 15~25g of potassium dichromate and slowly add it to In the above feed solution, react at a medium temperature of 38°C for 1.5h, slowly add a large amount of deionized water to dilute to about 1L, and control the temperature of the feed liquid below 100°C; filter after standing, and wash with a large amount of absolute ethanol and deionized water until the pH value is 3~4, dry for later use. Weigh nano-silica powder, micro-graphite oxide, and phenolic resin according to the design capacity of the composite material, dissolve them in an appropriate amount of absolute ethanol, ultrasonicate for 1 hour, stir for 2 hours, and then evaporate to dryness at 80°C. The Si/C composite negative electrode material is obtained after a high temperature treatment at 800° C. for 1 to 6 hours in a nitrogen or argon atmosphere.
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