CN104425805A - Tin carbon composite material, preparation method thereof and lithium-ion battery - Google Patents

Tin carbon composite material, preparation method thereof and lithium-ion battery Download PDF

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CN104425805A
CN104425805A CN 201310396148 CN201310396148A CN104425805A CN 104425805 A CN104425805 A CN 104425805A CN 201310396148 CN201310396148 CN 201310396148 CN 201310396148 A CN201310396148 A CN 201310396148A CN 104425805 A CN104425805 A CN 104425805A
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tin
composite material
carbon
carbon composite
core
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CN 201310396148
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朱广燕
刘三兵
翟丽娟
卢磊
海滨
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奇瑞汽车股份有限公司
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1393Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387Tin or alloys based on tin
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M2004/026Electrodes composed of or comprising active material characterised by the polarity
    • H01M2004/027Negative electrodes

Abstract

The invention discloses a tin carbon composite material, a preparation method thereof and a lithium-ion battery. The structure of the tin carbon composite material is a core-shell structure, wherein tin is utilized as a core of the core-shell structure, carbon is utilized as a shell of the core-shell structure, and a clearance exists between the core and the shell. According to the tin carbon composite material, the specific capacity is higher, the intercalation potential is low; compared with a silicon carbon composite material, the tin carbon composite material has the advantages that the electric conductivity is stronger due to the stronger electric conductivity of the tin. The tin carbon composite material is of the core-shell structure, the tin is utilized as the core of the core-shell structure, the carbon is utilized as the shell of the core-shell structure, and the clearance exists between the core and the shell; when the tin carbon composite material is utilized as a negative electrode material, the clearance can accommodate the volume expansion and shrinkage of the tin in charging and discharging processes, so that the volume effect of the tin is released, and the stability of the structure of the whole tin carbon composite material is enhanced; and therefore, the specific capacity of the tin carbon composite material is improved. The preparation method is simple and convenient to operate, and the lithium-ion battery is suitable for mass production.

Description

一种锡碳复合材料及其制备方法、锂离子电池 One tin-carbon composite material and its preparation method, a lithium ion battery

技术领域 FIELD

[0001] 本发明属于锂离子电池技术领域,具体涉及一种锡碳复合材料及其制备方法、锂离子电池。 [0001] The present invention belongs to the field of lithium ion battery technology, particularly relates to a tin-carbon composite material and its preparation method, a lithium ion battery.

背景技术 Background technique

[0002]目前,生产使用的锂离子电池主要采用石墨化碳为负极材料,但材料的储锂容量不高。 [0002] Currently, the production of the lithium ion battery using graphite carbon as a main negative electrode material, the lithium storage capacity of the material is not high. 就石墨基负极材料来说,其较大的层状结构空隙既为锂的储存提供了场所,也决定了该材料的低理论比容量(约372mAh/g)的特性。 On the graphite-based negative electrode materials, a layered structure of its larger voids provide a place to store only the lithium, but also determines the characteristics of the material is lower than the theoretical capacity (about 372mAh / g) of. 因此,开发新型的高容量和高倍率负极材料具有很高的研究和利用价值。 Therefore, the development of new high-capacity and high-rate cathode material has a high research and value in use. 负极材料研究发现如Sn、S1、Al、Sb等可与锂形成合金的金属或合金材料具有远远大于石墨的理论容量,引起了电池材料界的广泛关注。 As anode materials found Sn, S1, Al, Sb and the like may be alloyed with lithium metal or alloy having a theoretical capacity of graphite is much larger than, causing widespread concern in battery materials industry. 但该类材料具有很大的体积效应,导致在充放电过程中材料的粉化脱落,降低了电池的效率和循环性能。 However, such material has a large volume effects, resulting in shedding of powder material during charge and discharge, reducing the efficiency and cycle performance of the battery.

[0003] Sn基负极材料由于具有很高的理论克容量,低的嵌锂电位,较其他金属基材料有更高的稳定性而备受瞩目。 [0003] Sn-based negative electrode materials have high theoretical capacity of grams of low lithium intercalation potential than other metal-based material has a higher stability has attracted attention. 但Sn基负极材料与其他金属基材料一样,在脱嵌锂的过程中,存在着严重的体积效应,造成严重的安全隐患。 However, Sn-based negative electrode material with other metal-based material, as in the process of releasing lithium, there is a serious volume effect, causing a serious security risk. MYMa等人采用均匀沉淀法制备的SnO2-石墨复合材料具有不错的首次嵌锂容量,但首次库仑效率较低,容量衰减也比较快,这种方法也不能很好的解决Sn基负极材料在脱嵌锂过程中的体积效应(The Chinese Journal ofNonferrous Metals,Vol.15N0.5 (2005):793_798)。 MYMa, who used SnO2- graphite composite material prepared by homogeneous precipitation with good initial capacity of the oxide, the initial coulombic efficiency is low, relatively fast capacity fading, this method can not solve in the de-Sn-based negative electrode material volume effect lithium process (the Chinese Journal ofNonferrous Metals, Vol.15N0.5 (2005): 793_798). 王勇等人采用了原位合成法制备了一种锡-碳/核-壳结构的纳米粒子填充碳纳米管的锡碳复合材料,该材料的首次嵌锂容量达到了700mAh/g,循环性能有所提高,但材料制备工艺复杂,且难以控制,原料成本也较贵,难以达到实用化要求(王勇、焦正、吴明红等,一种制备锡-碳/核-壳结构的纳米粒子完全填充碳纳米管复合负极材料的原位合成方法,中国专利号:200910048318.6)。 Yong et al situ synthesis method using a tin - carbon / core - tin-carbon composite nanoparticles filled shell structure of carbon nanotubes, the initial capacity of the oxide material has reached 700mAh / g, cycle characteristics has increased, but the material preparation process is complicated and difficult to control, raw material costs are expensive, difficult to meet the practical requirements (Yong, n coke, red Wu, for the preparation of tin - carbon / core - shell structure nano-particles completely situ synthesis method of a carbon nanotube composite negative electrode material is filled, China patent number: 200910048318.6).

发明内容 SUMMARY

[0004] 本发明所要解决的技术问题是针对现有技术中存在的上述不足,提供一种锡碳复合材料及其制备方法、锂离子电池,该锡碳复合材料不仅具有较高的比容量,低的嵌锂电位,而且克服了锡的体积效应。 [0004] The present invention solves the technical problem of the prior art problems mentioned above present, there is provided a tin-carbon composite material and its preparation method, a lithium ion battery, the tin-carbon composite material not only having a high specific capacity, low lithium intercalation, and overcome the effects of the volume of tin.

[0005] 解决本发明技术问题所采用的技术方案是提供一种锡碳复合材料,该材料的结构为核壳结构,其中,锡为该核壳结构的核,碳为该核壳结构的壳,所述壳与所述核之间存在空隙。 [0005] Solving the Problem solutions employed in the present invention is to provide a tin-carbon composite material, the structural material is a core-shell structure, wherein the core shell structure for tin, carbon shell core-shell structure for , there is a gap between the shell and the core.

[0006] 优选的是,所述锡的粒径为10〜lOOnm。 [0006] Preferably, the particle size of the tin 10~lOOnm.

[0007] 优选的是,所述锡占所述锡碳复合材料的质量百分比为75〜95%。 [0007] Preferably, the percentage by mass of the tin of the tin accounts carbon composite material is 75~95%.

[0008] 优选的是,所述壳碳与所述核锡之间的空隙的体积与所述锡与所述碳的体积和的比为(1:9)〜(3:7)。 [0008] Preferably, the void volume of the housing between the carbon and the core of the tin with the tin and the volume of the carbon ratio (1: 9) to (3: 7).

[0009] 本发明提供一种锡碳复合材料的制备方法,包括以下步骤: [0009] The present invention provides a method of preparing tin-carbon composite material, comprising the steps of:

[0010] (I)将锡分散于不能将其溶解的溶剂中,再加入正硅酸乙酯(TE0S),所述正硅酸乙酯水解生成纳米的二氧化硅,得到二氧化硅包覆锡的复合材料; [0010] (I) dispersed in a tin can not be dissolved in a solvent, adding tetraethyl orthosilicate (TE0S), the positive nano silica TEOS hydrolysis to obtain silica-coated tin composite;

[0011] (2)在所述二氧化硅包覆锡的复合材料外包覆有机碳前躯体,在惰性气氛下进行灼烧,所述有机碳前躯体碳化成碳,得到在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料; [0011] (2) an outer coating of the silica-coated tin composite material of organic carbon precursor, firing performed under an inert atmosphere, prior to said carbonization of an organic carbon precursor into carbon, obtained dioxide an outer composite material coated with tin-coated composite silicon carbon material;

[0012] (3)加入碱腐蚀掉所述二氧化硅,得到锡碳复合材料,且所述锡与所述碳之间存在空隙。 [0012] (3) adding a base to the etched silicon dioxide, tin-carbon composite material obtained and there is a gap between the solder and the carbon.

[0013] 优选的是,所述步骤(I)加入所述正硅酸乙酯时,还加入能催化所述正硅酸乙酯水解的催化剂酸或催化剂碱。 [0013] Preferably, said step (I) was added to the TEOS, further addition of catalyst or an acid catalyst can catalyze base hydrolysis of the TEOS.

[0014] 优选的是,按所述锡占所述锡碳复合材料的质量百分比为75〜95%来确定所述有机碳前躯体的用量,所述空隙的体积与所述锡与所述碳的体积和的比为(1:9)〜(3:7)来确定所述正硅酸乙酯的用量。 [0014] Preferably, the percentage by mass of the tin of the tin accounts carbon composite material is 75~95% prior to said determining an amount of organic carbon precursor, the void volume of the tin to the carbon and the volume ratio of (1: 9) to (3: 7) to determine the amount of n-ethyl silicate.

[0015] 优选的是,所述步骤(I)中的所述催化剂酸为盐酸、硫酸、氢氟酸中的一种或几种; [0015] Preferably, the acid catalyst of the step (I) is one or more of hydrochloric acid, sulfuric acid, hydrofluoric acid;

[0016] 所述催化剂碱为氨水、氢氧化钠、碳酸钠中的一种或几种; [0016] The catalyst base is ammonia, sodium hydroxide, sodium carbonate, one or more of;

[0017] 所述溶剂为乙醇、异丙醇、正丁醇中的一种或几种;或者所述溶剂包括乙醇、异丙醇、正丁醇中的一种或几种,所述溶剂还包括水。 [0017] the solvent is ethanol, isopropanol, n-butanol is one or more; or the solvent comprises ethanol, isopropanol, n-butanol in one or several of said further solvent including water.

[0018] 优选的是,所述步骤(2)中灼烧时的加热温度为400〜600°C,加热时间为I〜5小时。 [0018] Preferably, the step (2) firing the heating temperature is 400~600 ° C, the heating time is I~5 hours.

[0019] 优选的是,所述步骤(2)中的所述有机碳前驱体为聚乙烯醇、丁苯橡胶乳、羧甲基纤维素钠、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、酚醛树脂、浙青、葡萄糖、蔗糖、纤维素、淀粉中的一种或几种。 [0019] Preferably, the step (2) in an organic carbon precursor is a polyvinyl alcohol, styrene-butadiene rubber milk, sodium carboxymethyl cellulose, polystyrene, polymethyl methacrylate, poly tetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, phenol resin, Zhejiang cyan, glucose, sucrose, cellulose, starch is one or more.

[0020] 优选的是,所述步骤(3)中的所述碱为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或几种;所述碱的浓度为I〜5M。 [0020] Preferably, the step of the base (3) is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate is one or more; the concentration of the alkali I~5M.

[0021] 本发明还提供一种锂离子电池,其负极包括上述的锡碳复合材料。 [0021] The present invention also provides a lithium ion battery, comprising a negative electrode the above-described tin-carbon composite material.

[0022] 通过本发明中的锡碳复合材料不仅具有较高的比容量,低的嵌锂电位,而且相对于硅碳复合材料来说,该锡碳复合材料中的锡不仅具有较高的比容量,而且其导电性更强,所以锡碳复合材料的导电性也更强。 [0022] Not only has a high specific capacity, low lithium intercalation in the present invention by a carbon-tin composite material, but also to silicon-carbon composite, the tin in the tin-carbon composite material not only has a higher ratio of capacity, and its more conductive, the conductive tin-carbon composite material is also stronger. 该锡碳复合材料为核壳结构,核为锡,壳为碳,核与壳之间存在空隙,当该锡碳材料作为负极材料时,上述空隙可以容纳充放电过程中锡的体积膨胀与收缩,缓解了锡的体积效应,增强了整个锡碳复合材料的结构的稳定性,从而提高了锡碳复合材料的比容量。 The tin-carbon composite material is a core - shell structure of tin, that there is a gap between the carbon shell, the core and the shell, when the tin-carbon material as a negative electrode material, the gap can be received through the charge and discharge of the volume of expansion and contraction Chengzhong Xi alleviate the effects of volume of tin, enhance the stability of the whole structure of a tin-carbon composite material, thereby increasing the specific capacity of the tin-carbon composite material. 本发明的制备方法,简单便于操作,适合大规模生产。 The preparation method is simple easy to operate, suitable for mass production.

附图说明 BRIEF DESCRIPTION

[0023] 图1是本发明实施例1中制备锡碳复合材料过程中材料结构变化的示意图; [0023] FIG. 1 is a schematic diagram of the production of tin-carbon composite material structural changes during an embodiment of the present invention;

[0024] 图2是本发明实施例1制备的锡碳复合材料制成的锂离子电池的充放电循环性能测试图。 [0024] FIG. 2 is a charge-discharge cycle performance test chart lithium ion battery made of tin-carbon composite prepared according to Example 1 of the present invention.

[0025] 图中:1-锡;2- 二氧化硅;3_碳;4_锡碳复合材料。 [0025] Numerals 1: tin; 2- silica; 3_ carbon; 4_ tin-carbon composite.

具体实施方式 Detailed ways

[0026] 为使本领域技术人员更好地理解本发明的技术方案,下面结合附图和具体实施方式对本发明作进一步详细描述。 [0026] to enable those skilled in the art better understand the technical solutions of the present invention, the following accompanying drawings and specific embodiments of the present invention will be described in further detail.

[0027] 实施例1 [0027] Example 1

[0028] 本实施例提供一种锡碳复合材料的制备方法,包括以下步骤: [0028] The present embodiment provides a method of preparing tin-carbon composite material, comprising the steps of:

[0029] (I)将Ig的粒径为20nm的锡颗粒加入到20ml水和80ml乙醇的混合溶剂中,超声分散30min,再加入2.08g的TE0S,此过程伴随连续搅拌,继续搅拌反应24h,TEOS水解生成S12,即得到二氧化硅包覆锡的复合材料。 [0029] (I) mixed solvent Ig 20nm particle diameter of tin particles were added to 20ml of water and 80ml of ethanol, the ultrasonic dispersion 30min, was added 2.08g of TE0S, the process with continuous stirring, reaction was stirred for 24h, TEOS hydrolysis S12, i.e., to obtain silica-coated tin composite material.

[0030] (2)将步骤(I)所得的二氧化硅包覆锡的复合材料与0.35g蔗糖通过球磨机干磨混合,将混合物转移到管式气氛炉中,在惰性气氛下灼烧,灼烧时的加热温度为450°C,加热时间为2h,自然冷却至室温得到在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料。 [0030] (2) the step (I) the composite silica-coated tin and 0.35g of sucrose obtained by dry milling a ball mill mixing, the mixture was transferred to a tubular atmosphere furnace, burning under an inert atmosphere, burning the heating temperature at firing is 450 ° C, the heating time was 2h, cooled to room temperature to obtain a composite material coated with a carbon material in the outer composite silica-coated tin.

[0031] (3)将步骤(2)所得在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料加入到过量的1mL的2M的氢氧化钠溶液中,并连续搅拌24h。 [0031] (3) Step (2) the resulting coated carbon material of the silica-coated outer composite tin composite 2M sodium hydroxide solution was added to 1mL of excess, and stirring continued for 24h. 将所得混合悬浮液过滤,并用蒸馏水洗涤,80°C干燥,即得到锡碳复合材料。 The resulting mixture suspension was filtered and washed with distilled water, 80 ° C and dried to obtain tin-carbon composite material. 其中,所述锡占所述锡碳复合材料的质量百分比为85%,所述壳碳与所述核锡之间的空隙的体积与所述锡与所述碳的体积和的比为1:9。 Wherein the percentage of the tin mass of the tin accounts carbon composite material was 85%, the void volume between the core and the shell carbon and the tin of the tin to carbon ratio of the volume and 1: 9.

[0032] 本实施例提供一种锡碳复合材料,其由上述制备方法得到。 [0032] The present embodiment provides a tin-carbon composite material obtained by the above production method.

[0033] 如图1所示,将锡I分散于不能将其溶解的溶剂中,加入正硅酸乙酯后,正硅酸乙酯在催化剂的作用下发生水解生成纳米的二氧化硅2,纳米的二氧化硅2包覆于锡I上,由于二氧化硅2为纳米颗粒且非常细小,所以在锡I上均匀包覆形成二氧化硅包覆锡的复合材料;在该复合材料外包覆碳3后形成在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料;用碱腐蚀掉二氧化硅2,得到锡碳复合材料4。 [0033] 1, I is dispersed in a tin can not be dissolved in a solvent, after the addition of TEOS, TEOS nano silica hydrolysis occurs under the action of the catalyst 2, nano-silica coated on the tin 2 I, 2 since the silica nanoparticles and very small, so the formation of tin-I uniformly coated composite silica-coated tin; outsourcing in the composite material after the carbon coating 3 is formed on an outer composite material of the silica-coated tin-coated composite material is carbon; etched away with an alkali silica 2 to give 4 carbon composite tin. 由于二氧化硅2在锡I与碳3之间,所以将二氧化硅2腐蚀掉后,在锡I与碳3之间形成空隙的体积约为被腐蚀掉的二氧化硅2的体积,通过该制备方法制备的锡碳复合材料4中的空隙的体积的大小可以通过在锡I上包覆不同体积的二氧化硅2来调节。 Since the silica I 2 between the tin and carbon 3, the etched silicon dioxide 2, the void volume formed between the tin and I volume of about 3 carbon silica 2 is etched by the size of the volume of tin 4 carbon composite material prepared by the preparation process of the different volumes of voids may be coated on the tin I 2 be adjusted by silica. 且由于二氧化硅2为纳米颗粒,所以可以通过碱对其进行腐蚀,本实施例中不可使用酸类溶液对二氧化硅2进行腐蚀,因为酸类溶液对二氧化硅2进行腐蚀时,也会同时腐蚀锡I。 2 and since the silica nanoparticles, the etching may be performed by a base thereof, the present embodiment can not be used in acid etching solution 2 of silica, because acid etching solution 2 silica, also It will also corrode tin I.

[0034] 通过该制备方法得到的锡碳复合材料4不仅具有较高的比容量,低的嵌锂电位,而且相对于硅碳复合材料来说,该锡碳复合材料4中的锡I不仅具有较高的比容量,而且其导电性更强,所以锡碳复合材料4的导电性也更强。 [0034] tin-carbon composite material obtained by the preparation process 4 not only has high specific capacity, low lithium intercalation, and silicon-carbon composite material with respect to it, the tin and tin 4 carbon composite material not only having I high specific capacity, and its more conductive, so that the conductive tin 4 carbon composite material is also stronger. 该锡碳复合材料4为核壳结构,核为锡1,壳为碳3,核与壳之间存在空隙,当该锡碳材料4作为负极材料时,上述空隙可以容纳充放电过程中锡I的体积膨胀与收缩,缓解了锡I的体积效应,增强了整个锡碳复合材料4的结构的稳定性,从而提高了锡碳复合材料4的比容量。 The tin-carbon composite material 4 is a shell structure, the core is a tin, a carbon shell 3, there is a gap between the core and the shell, when the tin 4 carbon material as a negative electrode material, the gap can accommodate discharge through Chengzhong Xi I volumetric expansion and contraction, to ease the effects of the volume of tin I, enhance the stability of the whole structure of a tin-carbon composite material 4, thereby increasing the specific capacity of the tin-carbon composite material 4. 本实施例中的制备方法,简单便于操作,适合大规模生产。 Prepared in the present embodiment, simple and easy to operate, suitable for mass production.

[0035] 电池的制作方法:将所制得的锡碳复合材料与导电剂乙炔黑、粘结剂PVDF(聚偏氟乙烯)按照质量比80: 10: 10混合均匀,用NMP (1-甲基-2-吡咯烷酮)将此混合物调制成浆料,均匀涂覆于铜箔上,放入烘箱中,在80°C下真空干燥24小时,制得实验电池用极片。 [0035] The manufacturing method of battery: The obtained tin-carbon composite material and the conductive agent, acetylene black, a binder PVDF (polyvinylidene fluoride) at a mass ratio of 80: 10 mixed with NMP (1- methyl: 10 yl 2-pyrrolidone) modulation and the mixture was a slurry, uniformly coated on a copper foil, placed in an oven, and dried in vacuo at 80 ° C 24 hours to obtain a test cell with a pole piece. 以锂片为对电极,电解液为lmol/L的LiPF6的EC (乙基碳酸酯)+DMC (二甲基碳酸酯)(体积比1:1)溶液,隔膜为celgard2400膜,在充满氩气气氛的手套箱内装配成CR2025型扣式电池。 Lithium sheets as the counter electrode, the electrolytic solution is EC lmol / L of LiPF6 in (ethyl carbonate) + DMC (dimethyl carbonate) (volume ratio 1: 1) solution, the separator is celgard2400 film, filled with argon atmosphere glove box assembled into CR2025 coin cell type.

[0036] 如图2所示,使用本实施例制得的锡碳复合材料制成扣式电池,并在恒流0.1C的条件下,对该电池进行充放电循环性能测试:该材料的首次放电比容量达到了813mAh/g,20次循环后比容量约为614mAh/g。 [0036] As shown, use is made of the present embodiment was prepared in Example tin-carbon composite material coin cell, a constant current of 0.1C and under the conditions of the battery charge and discharge cycle performance test 2: the first material discharge capacity reached 813mAh / g, the specific capacity after 20 cycles was about 614mAh / g.

[0037] 实施例2 [0037] Example 2

[0038] 本实施例提供一种锡碳复合材料的制备方法,包括以下步骤: [0038] The present embodiment provides a method of preparing tin-carbon composite material, comprising the steps of:

[0039] (I)将Ig的粒径为50nm的锡颗粒加入到20ml水、40ml乙醇、40ml异丙醇的混合溶剂中,超声分散30min,再加入3.12g的TE0S,并逐滴加入2ml浓硫酸作为催化剂,此过程伴随连续搅拌,继续搅拌反应24h,TEOS水解生成S12,即得到二氧化硅包覆锡的复合材料。 [0039] (I) the Ig tin particles having a particle diameter of 50nm was added to 20ml of water, 40ml of ethanol, 40ml of isopropanol in the mixed solvent, an ultrasonic dispersion 30min, was added 3.12g of TE0S, and added dropwise 2ml of concentrated sulfuric acid as a catalyst, this process, with continuous stirring, reaction was stirred for 24h, TEOS hydrolysis S12, i.e., to obtain silica-coated tin composite material. 上述水、乙醇、异丙醇的混合溶剂,有利于二氧化硅包覆锡的复合材料上的溶剂的挥发。 The above mixed solvent of water, ethanol, isopropanol, conducive to volatilization of the solvent on silica composite coating of tin.

[0040] (2)将步骤(I)所得的二氧化硅包覆锡的复合材料与含有0.67g酚醛树脂的乙醇溶液混合。 [0040] (2) The silica-coated tin composite material obtained in step (I) mixed with an ethanol solution containing 0.67g phenolic resin. 在搅拌条件下蒸干乙醇,在惰性气氛下灼烧,灼烧时的加热温度为600°C,加热时间为lh,自然冷却至室温得到在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料。 Ethanol was evaporated to dryness under stirring, calcined under an inert atmosphere, the heating temperature during firing is 600 ° C, the heating time is LH, cooled to room temperature to obtain a composite material in the silica-coated outer tin coated carbon composite.

[0041] (3)将步骤(2)所得所述二氧化硅包覆锡的复合材料外包覆碳的复合材料加入到30mL的IM的氢氧化钾溶液中,并连续搅拌48h。 [0041] (3) Step (2) The obtained composite silica outer cladding tin-coated composite material of carbon added to a solution of potassium hydroxide in 30mL of IM, and continuously stirred for 48h. 将所得混合悬浮液过滤,并用蒸馏水洗涤,60°C干燥,即得到锡碳复合材料。 The resulting mixture suspension was filtered and washed with distilled water, 60 ° C and dried to obtain tin-carbon composite material. 其中,所述锡占所述锡碳复合材料的质量百分比为75%,所述壳碳与所述核锡之间的空隙的体积与所述锡与所述碳的体积和的比为3:17。 Wherein the percentage of the tin mass of the tin accounts carbon composite material was 75%, the void volume between the core and the shell carbon and the tin of the tin and carbon volume ratio of 3: 17.

[0042] 本实施例提供一种锡碳复合材料,其由上述制备方法得到。 [0042] The present embodiment provides a tin-carbon composite material obtained by the above production method.

[0043] 按照实施例1中制备扣式电池的方法,使用本实施例制得的硅碳复合材料制成扣式电池,并按照实施例1同样的扣式电池测试方法,本实施例制得的材料首次放电比容量为770mAh/g,20次循环后,容量约为590mAh/g。 [0043] 1 prepared in accordance with Example coin cell, button cell prepared using the present embodiment prepared a silicon-carbon composite, and the same test method according to an embodiment of the button cell, the present embodiment prepared as described in Example material first discharge capacity was 770mAh / g, after 20 cycles, a capacity of about 590mAh / g.

[0044] 实施例3 [0044] Example 3

[0045] 本实施例提供一种锡碳复合材料的制备方法,包括以下步骤: [0045] The present embodiment provides a method of preparing tin-carbon composite material, comprising the steps of:

[0046] (I)将Ig的粒径为1nm的锡颗粒加入到10ml乙醇中,超声分散30min,再加入2.08g的TE0S,并逐滴加入2ml浓氨水作为催化剂,此过程伴随连续搅拌,继续搅拌反应24h,TEOS水解生成S12,即得到二氧化硅包覆锡的复合材料。 [0046] (I) The particle diameter of 1nm Ig tin particles were added to 10ml of ethanol, and ultrasonic dispersion 30min, was added 2.08g of TE0S, and 2ml of concentrated ammonia water was added dropwise as catalyst, this process, with continuous stirring, continued the reaction was stirred 24h, TEOS hydrolysis S12, i.e., to obtain silica-coated tin composite material.

[0047] (2)将步骤(I)所得的二氧化硅包覆锡的复合材料与含有0.5g聚乙烯醇的水溶液混合,在搅拌条件下蒸干,将混合物转移到管式气氛炉中,在惰性气氛下灼烧,灼烧时的加热温度为500°C,加热时间为5h,自然冷却至室温得到在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料。 [0047] (2) step of the composite material coated with silica, tin (I) obtained is mixed with an aqueous solution containing 0.5g of polyvinyl alcohol, evaporated to dryness under stirring, the mixture was transferred to a tube furnace atmosphere, firing under an inert atmosphere, the heating temperature during firing is 500 ° C, the heating time was 5h, cooled to room temperature to obtain a composite material of the outer silica-coated tin-coated composite carbon material.

[0048] (3)将步骤(2)所得在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料加入到1mL的4M的氢氧化钠溶液中,并连续搅拌12h。 [0048] (3) Step (2) The resulting carbon-coated composite material in the silica-coated outer composite material tin was added to 1mL of 4M sodium hydroxide solution, a continuously stirred 12h. 将所得混合悬浮液过滤,并用蒸馏水洗涤,70°C干燥,即得到锡碳复合材料。 The resulting mixture suspension was filtered and washed with distilled water, 70 ° C and dried to obtain tin-carbon composite material. 其中,所述锡占所述锡碳复合材料的质量百分比为80%,所述壳碳与所述核锡之间的空隙的体积与所述锡与所述碳的体积和的比为1:9。 Wherein the percentage of the tin mass of the tin accounts carbon composite material was 80%, the void volume between the core and the shell carbon and the tin of the tin to carbon ratio of the volume and 1: 9.

[0049] 本实施例提供一种锡碳复合材料,其由上述制备方法得到。 [0049] The present embodiment provides a tin-carbon composite material obtained by the above production method.

[0050] 按照实施例1中制备扣式电池的方法,使用本实施例制得的硅碳复合材料制成扣式电池,并按照实施例1同样的扣式电池测试方法,本实施例制得的材料首次放电比容量为840mAh/g,20次循环后,容量约为608mAh/g。 [0050] 1 prepared in accordance with Example coin cell, button cell prepared using the present embodiment prepared a silicon-carbon composite, and the same test method according to an embodiment of the button cell, the present embodiment prepared as described in Example material first discharge capacity was 840mAh / g, after 20 cycles, a capacity of about 608mAh / g.

[0051] 实施例4 [0051] Example 4

[0052] 本实施例提供一种锡碳复合材料的制备方法,包括以下步骤: [0052] The present embodiment provides a method of preparing tin-carbon composite material, comprising the steps of:

[0053] (I)将Ig的粒径为40nm的锡颗粒加入到30ml乙醇、40ml异丙醇、30ml正丁醇的混合溶剂中,超声分散30min,再加入16g的TE0S,此过程伴随连续搅拌,继续搅拌反应24h,TEOS水解生成S12,即得到二氧化硅包覆锡的复合材料。 [0053] (I) of the Ig 40nm particle size of tin particles were added to 30ml of ethanol, 40ml of isopropanol, a mixed solvent of n-butanol 30ml, ultrasonic dispersion 30min, then add 16g of TE0S, this process is accompanied by continuous stirring , the reaction was stirred 24h, TEOS hydrolysis S12, i.e., to obtain silica-coated tin composite material.

[0054] (2)将步骤(I)所得的二氧化硅包覆锡的复合材料与Ig葡萄糖和Ig的羧甲基纤维素在球磨机中球磨混合均匀。 [0054] (2) The silica-coated tin composite material obtained in step (I) with Ig and Ig glucose carboxymethyl cellulose uniformly mixed in a ball mill in a ball mill. 将混合物转移到管式气氛炉中,400°C保温5h,自然冷却至室温得到在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料。 The mixture was transferred to a tube furnace atmosphere, 400 ° C heat 5h, cooled to room temperature to obtain a composite material coated with a carbon material in the outer composite silica-coated tin.

[0055] (3)将步骤(2)所得在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料加入到SmL的5M的氢氧化钠溶液中,并连续搅拌10h。 Composite material [0055] (3) Step (2) the resulting coated carbon composite material outside the silica-coated tin was added to a 5M solution of sodium hydroxide in SmL and continuously stirred for 10h. 将所得混合悬浮液过滤,并用蒸馏水洗涤,80°C干燥,即得到锡碳复合材料。 The resulting mixture suspension was filtered and washed with distilled water, 80 ° C and dried to obtain tin-carbon composite material. 其中,所述锡占所述锡碳复合材料的质量百分比为95%,所述壳碳与所述核锡之间的空隙的体积与所述锡与所述碳的体积和的比为9:41。 Wherein the percentage of the tin mass of the tin accounts carbon composite material was 95%, the void volume between the core and the shell carbon and the tin of the tin to carbon ratio of volume and 9: 41.

[0056] 本实施例提供一种锡碳复合材料,其由上述制备方法得到。 [0056] The present embodiment provides a tin-carbon composite material obtained by the above production method.

[0057] 按照实施例1中制备扣式电池的方法,使用本实施例制得的硅碳复合材料制成扣式电池,并按照实施例1同样的扣式电池测试方法,本实施例制得的材料首次放电比容量为749mAh/g,20次循环后,容量约为623mAh/g。 [0057] 1 prepared in accordance with Example coin cell, button cell prepared using the present embodiment prepared a silicon-carbon composite, and the same test method according to an embodiment of the button cell, the present embodiment prepared as described in Example material first discharge capacity was 749mAh / g, after 20 cycles, a capacity of about 623mAh / g.

[0058] 实施例5 [0058] Example 5

[0059] 本实施例提供一种锡碳复合材料的制备方法,包括以下步骤: [0059] The present embodiment provides a method of preparing tin-carbon composite material, comprising the steps of:

[0060] (I)将Ig的粒径为10nm的锡颗粒加入到20ml水、40ml异丙醇、40ml正丁醇的混合溶剂中,超声分散30min,再加入7.86g的TE0S,并逐滴加入2ml的2M的氢氧化钠溶液和2ml的IM的碳酸钠溶液作为催化剂,此过程伴随连续搅拌,继续搅拌反应24h,TE0S水解生成S12,即得到二氧化硅包覆锡的复合材料。 [0060] (I) to a particle size of 10nm Ig tin particles are added to 20ml of water, 40ml of isopropanol, a mixed solvent of n-butanol 40ml, ultrasonic dispersion 30min, was added 7.86g of TE0S, and added dropwise 2ml of 2M sodium hydroxide solution and 2ml of IM sodium carbonate solution as a catalyst, the process with continuous stirring, reaction was stirred for 24h, TE0S hydrolysis S12, i.e., to obtain silica-coated tin composite material.

[0061] (2)将步骤(I)所得的二氧化硅包覆锡的复合材料与含有0.5g 丁苯橡胶乳的水溶液混合均匀,搅拌下蒸干,将混合物转移到管式气氛炉中,在惰性气氛下灼烧,灼烧时的加热温度为500°C加热时间为4h,自然冷却至室温得到在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料。 [0061] (2) step of the composite material coated with silica, tin (I) obtained with a mixed aqueous solution containing 0.5g of styrene-butadiene rubber uniform milk, evaporated to dryness under stirring, the mixture was transferred to a tube furnace atmosphere, firing under an inert atmosphere, the heating temperature during firing is 500 ° C the heating time was 4h, cooled to room temperature to obtain a composite material of the outer silica-coated tin-coated composite carbon material.

[0062] (3)将步骤(2)所得在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料加入到1mL的4M的碳酸钾溶液中,并连续搅拌10h。 [0062] (3) Step (2) The resulting carbon-coated composite material in the silica-coated outer composite material tin was added to a solution of potassium carbonate in 1mL of 4M, and continuously stirred for 10h. 将所得混合悬浮液过滤,并用蒸馏水洗涤,80°C干燥,即得到锡碳复合材料。 The resulting mixture suspension was filtered and washed with distilled water, 80 ° C and dried to obtain tin-carbon composite material. 其中,所述锡占所述锡碳复合材料的质量百分比为90%,所述壳碳与所述核锡之间的空隙的体积与所述锡与所述碳的体积和的比为3:7。 Wherein the percentage of the tin mass of the tin accounts carbon composite material was 90%, the void volume between the core and the shell carbon and the tin of the tin and carbon volume ratio of 3: 7.

[0063] 本实施例提供一种锡碳复合材料,其由上述制备方法得到。 [0063] The present embodiment provides a tin-carbon composite material obtained by the above production method.

[0064] 按照实施例1中制备扣式电池的方法,使用本实施例制得的硅碳复合材料制成扣式电池,并按照实施例1同样的扣式电池测试方法,本实施例制得的材料首次放电比容量为804mAh/g,20次循环后,容量约为583mAh/g。 [0064] 1 prepared in accordance with Example coin cell, button cell prepared using the present embodiment prepared a silicon-carbon composite, and the same test method according to an embodiment of the button cell, the present embodiment prepared as described in Example material first discharge capacity was 804mAh / g, after 20 cycles, a capacity of about 583mAh / g.

[0065] 可以理解的是,以上实施方式仅仅是为了说明本发明的原理而采用的示例性实施方式,然而本发明并不局限于此。 [0065] It will be appreciated that the above embodiments are merely illustrative of the principles of the present invention is employed in an exemplary embodiment, but the present invention is not limited thereto. 对于本领域内的普通技术人员而言,在不脱离本发明的精神和实质的情况下,可以做出各种变型和改进,这些变型和改进也视为本发明的保护范围。 For those of ordinary skill in the art, without departing from the spirit and substance of the invention can be made various modifications and improvements, these modifications and improvements into the protection scope of the invention.

Claims (11)

1.一种锡碳复合材料,其特征在于,该材料的结构为核壳结构,其中,锡为该核壳结构的核,碳为该核壳结构的壳,所述壳与所述核之间存在空隙。 A tin-carbon composite material, characterized in that the structure of the core-shell structure material, wherein the tin for the core-shell structure that the shell core core-shell structure, the carbon, the shell and the core of between the presence of voids.
2.根据权利要求1所述的锡碳复合材料,其特征在于,所述锡的粒径为10〜lOOnm。 The tin-carbon composite material according to claim 1, wherein the particle size of the tin 10~lOOnm.
3.根据权利要求1所述的锡碳复合材料,其特征在于,所述锡占所述锡碳复合材料的质量百分比为75〜95%。 3. The tin-carbon composite material according to claim 1, characterized in that the percentage by mass of the tin of the tin accounts carbon composite material is 75~95%.
4.根据权利要求1所述的锡碳复合材料,其特征在于,所述壳碳与所述核锡之间的空隙的体积与所述锡与所述碳的体积和的比为(1:9)〜(3:7)。 The tin-carbon composite material according to claim 1, wherein the void volume between the core and the shell carbon and the tin of the tin and the volume ratio of carbon (1: 9) to (3: 7).
5.一种权利要求1所述的锡碳复合材料的制备方法,其特征在于,包括以下步骤: (1)将锡分散于不能将其溶解的溶剂中,再加入正硅酸乙酯,所述正硅酸乙酯水解生成纳米的二氧化硅,得到二氧化硅包覆锡的复合材料; (2)在所述二氧化硅包覆锡的复合材料外包覆有机碳前躯体,在惰性气氛下进行灼烧,所述有机碳前躯体碳化成碳,得到在所述二氧化硅包覆锡的复合材料外包覆碳的复合材料; (3)加入碱腐蚀掉所述二氧化硅,得到锡碳复合材料,且所述锡与所述碳之间存在空隙。 Preparation of tin-carbon composite material A according to claim 1, characterized by comprising the steps of: (1) dispersed in a tin can not be dissolved in a solvent, TEOS was added, the said TEOS hydrolysis-silica generates nm, to obtain silica-coated tin composite material; (2) coated with an organic carbon precursor in the silica-coated outer composite material of tin, in an inert atmosphere for firing, the organic carbon precursor carbonized into carbon, carbon composite material is obtained in the outer coating of the silica-coated tin composite material; and (3) adding a base to the silica is etched away, tin-carbon composite material obtained and there is a gap between the solder and the carbon.
6.根据权利要求5所述的锡碳复合材料的制备方法,其特征在于,按所述锡占所述锡碳复合材料的质量百分比为75〜95%来确定所述有机碳前躯体的用量,所述空隙的体积与所述锡与所述碳的体积和的比为(1:9)〜(3:7)来确定所述正硅酸乙酯的用量。 6. The method of preparation of tin-carbon composite material according to claim 5, characterized in that the percentage by mass of the tin of the tin accounts carbon composite material is 75~95% prior to said determining an amount of organic carbon precursor , the volume of the void volume of the tin and the ratio of carbon (1: 9) to (3: 7) to determine the amount of n-ethyl silicate.
7.根据权利要求5所述的锡碳复合材料的制备方法,其特征在于,所述步骤(I)中的所述溶剂为乙醇、异丙醇、正丁醇中的一种或几种;或者所述溶剂包括乙醇、异丙醇、正丁醇中的一种或几种,所述溶剂还包括水。 The production method according to tin 5 carbon composite material as claimed in claim, characterized in that the solvent of the step (I) in ethanol, isopropanol, one or more of n-butanol; or the solvent comprises ethanol, isopropanol, n-butanol one or more, the solvent further comprises water.
8.根据权利要求5所述的锡碳复合材料的制备方法,其特征在于,所述步骤(2)中灼烧时的加热温度为400〜600°C,加热时间为I〜5小时。 8. A method of preparing tin-carbon composite material according to claim 5, wherein the heating temperature during burning (2) in said step is 400~600 ° C, the heating time is I~5 hours.
9.根据权利要求5所述的锡碳复合材料的制备方法,其特征在于,所述步骤(2)中的所述有机碳前驱体为聚乙烯醇、丁苯橡胶乳、羧甲基纤维素钠、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、酚醛树脂、浙青、葡萄糖、蔗糖、纤维素、淀粉中的一种或几种。 9. The production method according to tin 5 carbon composite material as claimed in claim, wherein said step (2) in an organic carbon precursor is a polyvinyl alcohol, styrene-butadiene rubber milk, carboxymethyl cellulose sodium, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, phenol resin, Zhejiang cyan, glucose, sucrose, cellulose, starch is one or more.
10.根据权利要求5所述的锡碳复合材料的制备方法,其特征在于,所述步骤(3)中的所述碱为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的一种或几种;所述碱的浓度为I〜5M。 10. A method of preparing tin-carbon composite material according to 5 claim, wherein said step of said base (3) is sodium hydroxide A potassium hydroxide, sodium carbonate, potassium carbonate or more; the concentration of the alkali I~5M.
11.一种锂离子电池,其特征在于,其负极包括权利要求1〜4任意一项所述的锡碳复合材料。 A lithium-ion battery, characterized in that the tin-carbon composite negative electrode material according to claim 1 ~ 4 comprises any.
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