WO2002027822A1

WO2002027822A1 - Nanometer metal or nanometer alloy/carbon composite material, producing method thereof and the application thereof in a secondary lithium battery

Info

Publication number: WO2002027822A1
Application number: PCT/CN2001/000918
Authority: WO
Inventors: Hong Li; Lihong Shi; Qing Wang; Xuejie Huang; Liquan Chen
Original assignee: Institute Of Physics, Chinese Academy Of Sciences
Priority date: 2000-06-06
Filing date: 2001-06-06
Publication date: 2002-04-04
Also published as: CN1327275A; CN1151570C

Abstract

The invention relates to a nanometer metal or nanometer alloy/carbon composite material, producing method thereof and the application thereof in a secondary lithium battery. The composite material is manufactured by a co-reducing method in an organic solvent system. The nanometer metal or nanometer alloy particles are deposited onto the outer surface and inner surface of the carbon particles having pore structure. A mean particle size of the nanometer metal or nanometer alloy particles is 1-250 nm, a mean particle size of the carbon particles is 1-50 nm and a weight percent of the nanometer metal or nanometer alloy particle to the carbon particle is 10 %-70 %. The secondary lithium battery which uses the composite material as a negative active material has high reversible capacity, excellent cycle characteristics, reliable safety and resistance to high current charge-discharge.

Description

纳米金属或鈉米合金 /碳复合材料及其制备方法与在二次锂电池中的应用 Nano metal or sodium rice alloy / carbon composite material, preparation method thereof and application in secondary lithium battery

发明领域 Field of invention

本发明涉及金属或合金 /碳复合材料及其制备方法与应用，特别是涉及纳米金属或纳米合金 /碳复合材料及其制备方法与在二次锂电池中的应用。 The present invention relates to a metal or alloy / carbon composite material and a preparation method and application thereof, and particularly to a nano metal or nano alloy / carbon composite material, a preparation method thereof, and application in a secondary lithium battery.

背景技术 Background technique

相对于一般碳材料而言，纳米金属 /碳复合材料在磁性能、电性能和吸附性能方面具有突出的优点。纳米金属分散在碳材料的表面或内部孔结构中，可以减少纳米金属的氧化，提高纳米金属的稳定性。因此纳米金属 /碳复合材料可以结合纳米金属与碳材料的优点，具有广泛的应用前景。但目前的纳米金属 /碳复合材料中纳米金属多为具有催化活性的 Fe、 Co、 Ni、 Pt或 Pd等金属，其他金属或合金在专利和公开发表的文献中报道较少。 Compared with general carbon materials, nano-metal / carbon composites have outstanding advantages in terms of magnetic properties, electrical properties and adsorption properties. Nano-metals are dispersed in the surface or internal pore structure of carbon materials, which can reduce the oxidation of nano-metals and improve the stability of nano-metals. Therefore, nano metal / carbon composite materials can combine the advantages of nano metal and carbon materials, and have broad application prospects. However, in the current nano-metal / carbon composite materials, most of the nano-metals are catalytically active metals such as Fe, Co, Ni, Pt or Pd, and other metals or alloys are reported less in patents and published literature.

目前制备金属 /碳复合材料的方法主要包括 (1)液相浸渍法，把碳与金属盐溶液混合，然后过滤，于燥，还原；（2)气相沉积法，碳粒子与金属蒸汽相接触；（3)利用有机金属化合物、高分子金属络合物或有机金属聚合物作为前驱体进行炭化热解；（4)共沉淀方法，把碳与金属盐水溶液混合，在液相中将其还原。其中方法 (2) 和 (3)可以得到纳米级的金属颗粒（小于 100纳米）与碳的复合材料，但负载量较低，成本较高。方法 (1)得到的纳米金属 /碳复合材料目前主要为高熔点的贵金属与碳形成的复合材料，负载量较低。方法 (4)得到的金属颗粒尺寸较大，分散不均勾。以上在陈学刚等发表的《碳素技术》 2000年第 5期第 16页的综述中有所介绍。 The current methods for preparing metal / carbon composite materials mainly include (1) a liquid phase impregnation method, mixing carbon with a metal salt solution, then filtering, drying, and reducing; (2) a vapor deposition method, in which carbon particles are in contact with metal vapor; (3) Carbonization pyrolysis using an organometallic compound, a polymer metal complex or an organometallic polymer as a precursor; (4) A co-precipitation method in which carbon is mixed with an aqueous solution of a metal salt and reduced in a liquid phase. Among them, methods (2) and (3) can obtain nanometer-scale metal particles (less than 100 nanometers) and carbon composite materials, but the load is lower and the cost is higher. The nanometal / carbon composite material obtained by method (1) is mainly a composite material of noble metal with high melting point and carbon, and the load is low. The metal particles obtained by method (4) are large in size and unevenly dispersed. The above is introduced in the review of Carbon Technology, Issue 5, 2000, published by Chen Xuegang et al.

金属或合金可以在二次锂电池中作为负极活性材料使用，并且具有很高的储锂容量。在七十年代初到八十年代末，锂铝、锂硅、锂铅、锂锡、锂镉等锂合金曾用于二次锂电池负极活性材料。但这些合金在反复充放电过程中由于体积膨胀和收缩而逐渐粉化，导致合金微粒与集流体之间以及合金微粒之间的电接触变差，电池性能很快变坏甚至失效，如 K. M. Abraham 在《电化学通讯》 ( iElectrochemica. Acta.!) ) , Vol. 138, 1233(1993)中所叙述。为了解决合金在充放电过程中的粉化问题，最近，我们提出采用超细金属或合金体系作为负极活性材料，超细合金颗粒具有较好的塑性，承受在充放电过程中因体积变化而带来的应力变化的能力较强，因此与较大尺寸的合金材料相比，其循环性有明显改善，如李泓在中国专利 CN 97112460.4(1997年)中所述。但进一歩的研究表明，由于超细合金负极材料具有较大的表面能，在充放电过程中会逐渐团聚成尺寸达微米级的颗粒，导致其长期循环性变差，动力学优势丧失，如李泓在《固态离子》 ( iSolid State Ionics》 ) ， VOL135-137, 181-192(2000)中所述。 Metals or alloys can be used as negative electrode active materials in secondary lithium batteries and have high lithium storage capacity. From the early 1970s to the end of the 1980s, lithium alloys such as lithium aluminum, lithium silicon, lithium lead, lithium tin, and lithium cadmium were used as negative electrode active materials for secondary lithium batteries. However, these alloys gradually pulverized due to volume expansion and contraction during repeated charge and discharge processes, resulting in poor electrical contact between alloy particles and current collectors and between alloy particles, and battery performance quickly deteriorated or even failed, such as KM Abraham As described in "Electrochemica. Acta.!", Vol. 138, 1233 (1993). In order to solve the problem of pulverization of the alloy during the charge and discharge process, recently, we proposed the use of ultra-fine metal or alloy system as the negative electrode active material. The ultra-fine alloy particles have good plasticity and can withstand band changes due to volume changes during the charge and discharge process. The ability to change the stress in the future is stronger, so compared with the alloy material with larger size, its cyclicity is significantly improved, As described by Li Hong in Chinese Patent CN 97112460.4 (1997). However, further research shows that due to the large surface energy of ultrafine alloy anode materials, they will gradually agglomerate into micron-sized particles during charge and discharge, resulting in poor long-term cycling and loss of kinetic advantages, such as Li Hong, "Solid State Ionics", VOL135-137, 181-192 (2000).

发明的公开 Disclosure of invention

本发明的目的在于克服已有纳米合金材料稳定性差的缺点，提供一种新的结构和化学性质稳定的纳米金属或纳米合金 /碳复合材料；本发明的另一目的是提供一种工艺简单、成本低，适于大规模生产，而且制备的纳米金属或纳米合金颗粒尺寸约为 100纳米，分散均匀，与碳材料的附着性好的，在有机溶剂体系中共还原制备纳米金属或纳米合金 /碳复合材料的方法；本发明进一歩的目的是提供这种纳米金属或纳米合金 /碳复合材料的用途，特别是这种复合材料解决了纳米金属或纳米合金在充放电过程中的电化学团聚问题，作为二次锂电池负极材料的应用，使锂电池具有良好的循环特性和安全性，且具有较高的能量密度。 The object of the present invention is to overcome the shortcomings of the poor stability of existing nano-alloy materials and provide a new nano-metal or nano-alloy / carbon composite material with stable structure and chemical properties. Another object of the present invention is to provide a simple process, Low cost, suitable for large-scale production, and the prepared nano-metal or nano-alloy particles are about 100 nanometers in size, uniformly dispersed, and good adhesion to carbon materials. Co-reduction in organic solvent systems to prepare nano-metals or nano-alloys / carbon Method of composite material; A further object of the present invention is to provide the use of such a nano-metal or nano-alloy / carbon composite material, in particular, this composite material solves the problem of electrochemical agglomeration of nano-metal or nano-alloy during charging and discharging The application as a negative electrode material of a secondary lithium battery enables the lithium battery to have good cycle characteristics and safety, and has a high energy density.

本发明的目的是这样实现的： The object of the present invention is achieved as follows:

本发明所提供的纳米金属或纳米合金 /碳复合材料包括：纳米金属或纳米合金颗粒沉积在碳颗粒的外表面和碳颗粒所含内部孔的孔腔或孔壁中（即内表面），其中纳米金属或纳米合金颗粒的平均尺寸为 l~250nm，碳颗粒的平均尺寸为 lum~50um, 纳米金属或纳米合金颗粒与碳颗粒的重量百分比为 10%~70%。 The nano-metal or nano-alloy / carbon composite material provided by the present invention comprises: nano-metal or nano-alloy particles are deposited on the outer surface of the carbon particles and the pore cavity or pore wall (ie, the inner surface) of the inner pores contained in the carbon particles, wherein the nano-metal Or the average size of nano-alloy particles is 1 ~ 250nm, the average size of carbon particles is lum ~ 50um, and the weight percentage of nano-metal or nano-alloy particles and carbon particles is 10% -70%.

所述的纳米金属为 Sn、 Sb、 In或 Zn之中的任意一种。 The nano metal is any one of Sn, Sb, In or Zn.

所述的纳米合金的表达式定义为 M^M^^ .M¹^, 其中 M M²...Mⁿ表示不同的元素，并至少含有 Sn、 Sb、 In或 Zn之中的任意一种，也可以含有主族元素中的 Mg、 B、 Al、 Si及过渡金属族的 Ti、 V、 Mn、 Fe、 Co、 Ni、 Cu或 Ag等；其中下标 xl、 χ2...χη代表不同元素原子占纳米合金所有元素原子总摩尔数的摩尔百分比， xl+x2+...+xn=l , χΚ χ2、 ...χη的取值为 0~1之间，且 Sn、 Sb、 In或 Zn四种元素摩尔百分比的和不低于 50%; 其中 n为 1~16的整数。 The expression nanoalloys defined as M ^ M ^^ .M ¹ ^, wherein MM ² ... M ⁿ represent different elements, and containing at least any from among Sn, Sb, In or Zn one of It can also contain Mg, B, Al, Si in the main group elements, and Ti, V, Mn, Fe, Co, Ni, Cu, or Ag in the transition metal group; where the subscripts xl, χ2 ... χη represent different elements The mole percentage of atoms in the total number of moles of all the atoms of the nano-alloy, xl + x2 + ... + xn = l, χΚ χ2, ... χη are between 0 ~ 1, and Sn, Sb, In or Zn The sum of the mole percentages of the four elements is not less than 50%; where n is an integer from 1 to 16.

所述的碳材料可以是石墨类碳或非石墨类碳。 The carbon material may be graphite-based carbon or non-graphite-based carbon.

本发明所提供的纳米金属或纳米合金 /碳复合材料还包括在纳米金属或纳米合金 /碳复合材料中含有少量氧，氧元素占该复合材料的重量百分比为 0.001%-10%。这是由于纳米金属或纳米合金比较活泼，在制备、保存和转移过程中其表面不可避免地会发生氧化，因此可允许少量氧存在。 The nano-metal or nano-alloy / carbon composite material provided by the present invention further includes a small amount of oxygen in the nano-metal or nano-alloy / carbon composite material, and the weight percentage of oxygen element in the composite material is 0.001% -10%. This is because nanometals or nanoalloys are relatively active, and their surfaces inevitably undergo oxidation during preparation, storage, and transfer, so a small amount of oxygen can be allowed to exist.

本发明的纳米金属或纳米合金 /碳复合材料，其中纳米合金例如 Sn。. ^Sb^合金、 Sn。_S8Sb_{Q 12}合金、 8 ₄₄81¾₁₆。_¾4合金或8 ₄2_¾550。.。₅合金，纳米金属 Sb、 In、 Sn 或 Zn均符合本发明的要求。 Sno.₈₈Sb。,₂合金其实际组成可以为 S_¾76/(SnSb)。.₁₂的两相混合，也可以为 Sn。_S8/Sb。.₁₂的两相混合。而纳米合金例如 S¾₄₉C¾₅₁和纳米金属 Sn。.₈₈0。, lj不符合本发明要求。 The nano metal or nano alloy / carbon composite material of the present invention, wherein the nano alloy is, for example, Sn. . ^ Sb ^ 合 Gold, Sn. _S8 Sb _{Q 12} alloy, 8 ₄₄ 81¾ ₁₆ . _¾4 alloy or 8 ₄ 2 _¾55 0. .. ₅ alloy, nano metal Sb, In, Sn or Zn all meet the requirements of the present invention. Sno. ₈₈ Sb. The actual composition of the ₂ alloy can be S _¾76 / (SnSb). The two-phase mixture of ₁₂ can also be Sn. _S8 / Sb. . ₁₂ two-phase mixture. And nano alloys such as S¾ ₄₉ C¾ ₅₁ and nano metal Sn. . ₈₈ 0. , lj does not meet the requirements of the present invention.

所述的碳材料可以是石墨类碳或非石墨类碳，优选天然石墨、石墨化中间相碳小球、针状焦、碳纤维或微孔硬碳球。碳颗粒平均尺寸为 lum~50um，可以为无孔的碳材料，也可以含有大量微孔。这些碳颗粒能够可逆地嵌入和脱出锂离子。该碳材料通过 Brunauer- Emmett-Teller (以下简称 BET方法）方法测定的比表面积在 0.1-3000 m²/g，其中外表面积为 0.1-50m²/g，所含孔的表面积（内表面积)为 0.1- The carbon material may be graphite-based carbon or non-graphite-based carbon, and is preferably natural graphite, graphitized mesophase carbon pellets, needle coke, carbon fiber, or microporous hard carbon pellets. The average size of carbon particles is lum ~ 50um, which can be a non-porous carbon material, or it can contain a large number of micropores. These carbon particles are capable of reversibly inserting and extracting lithium ions. The carbon material by Brunauer- Emmett-Teller (hereinafter referred to as BET method) Method of measuring specific surface area of 0.1-3000 m ² / g, wherein the external surface area of 0.1-50m ² / g, a surface area contained in the pores (the surface area) 0.1-

本发明的纳米金属或纳米合金 /碳复合材料中，大部分纳米金属或纳米合金颗粒与碳颗粒的外表面或内部所含孔的内表面直接接触，内外表面纳米金属或纳米合金所占的比例不受限制。在纳米金属或纳米合金 /碳复合材料中，不和碳颗粒的外表面直接接触，处于游离状态的纳米金属或纳米合金占复合材料中纳米金属或合金总重量的 0.1-30%。 In the nano-metal or nano-alloy / carbon composite material of the present invention, most of the nano-metal or nano-alloy particles are in direct contact with the outer surface of the carbon particles or the inner surface of the pores contained therein. The proportion of the inner-outer surface nano-metal or nano-alloy Unlimited. In nanometals or nanoalloys / carbon composites, the nanometals or nanoalloys in the free state do not directly contact the outer surface of the carbon particles, and they account for 0.1-30% of the total weight of the nanometals or alloys in the composite.

图 3(A)、（B)、（C)为本发明的纳米金属或纳米合金 /碳复合材料的扫描电镜照片，可以清楚地看到纳米尺度的合金颗粒均匀分散在碳颗粒的外表面，游离的合金颗粒非常少。 3 (A), (B), and (C) are scanning electron microscope photographs of the nanometal or nanoalloy / carbon composite material of the present invention, and it can be clearly seen that nanoscale alloy particles are uniformly dispersed on the outer surface of the carbon particles. There are very few free alloy particles.

本发明所提供的纳米金属或纳米合金 /碳复合材料，可以通过在有机溶剂体系中共还原的技术制备，具体步骤如下： The nano metal or nano alloy / carbon composite material provided by the present invention can be prepared by a co-reduction technique in an organic solvent system, and the specific steps are as follows:

1. 反应液配制: 1. Reaction solution preparation:

( 1 ) 配制氯化物溶液：将一种或几种氯化物混合后，溶于一种 C1-C4的醇中，形成浓度为 0.01~3M的氯化物溶液； (1) preparing a chloride solution: after mixing one or more chlorides, dissolving in a C1-C4 alcohol to form a chloride solution having a concentration of 0.01 to 3M;

其中氯化物为 Sn、 Sb、 In、 Zn或主族元素中的 Mg、 B、 Al、 Si或过渡金属族元素中的 Ti、 V、 Mn、 Fe、 Co、 Ni、 Cu、 Ag的氯化物，并至少含有 Sn、 Sb、 In或 Zn氯化物中的一种，且 Sn、 Sb、 In或 Zn的氯化物占所有氯化物的摩尔百分比的和不低于 50%。 Wherein the chloride is a chloride of Sn, Sb, In, Zn or Mg, B, Al, Si in the main group element or Ti, V, Mn, Fe, Co, Ni, Cu, Ag in the transition metal group element, It contains at least one of the chlorides of Sn, Sb, In or Zn, and the sum of the molar percentages of the chlorides of Sn, Sb, In or Zn to all chlorides is not less than 50%.

(2) 配制还原悬浊液：将上述氯化物溶液中的阳离子全部还原为单质所需化学计量的 90%~105%量的 Zn粉、 Fe粉、 Mg粉或 A1粉中一种，加入到上述（1 ) 相同的 C1-C4的醇中，所用醇的体积与氯化物溶液的体积比为 0.001-200，形成悬浊液，其中 Zn粉、 Fe粉、 Mg粉或 A1粉颗粒尺寸为 20nm-50um。 2. 在有机溶剂体系中共还原： (2) Preparation of reduction suspension: All the cations in the above chloride solution are reduced to one of Zn powder, Fe powder, Mg powder or A1 powder in the amount of 90% to 105% of the stoichiometry required for the element, and added to In the same C1-C4 alcohol (1) above, the volume ratio of the volume of the alcohol to the chloride solution is 0.001-200 to form a suspension, wherein the particle size of the Zn powder, Fe powder, Mg powder or A1 powder is 20 nm -50um. 2. Co-reduction in organic solvent systems:

包括将碳粉加入上述歩骤 1配制的氯化物溶液中，在 -20°C〜200°C的温度下，在 lmin-24h之内，用分液漏斗将上述步骤 1配制的还原悬浊液全部滴加到氯化物溶液中，并同时搅拌； It includes adding carbon powder to the chloride solution prepared in step 1 above, and at a temperature of -20 ° C ~ 200 ° C, within 1min-24h, using a separatory funnel, the reduction suspension prepared in step 1 above. Add all to the chloride solution with stirring;

或者将碳粉加入上述歩骤 1配制的还原悬浊液中，在 -20°C~200°C的温度下，在 lmin-24h时间内，用分液漏斗将上述歩骤 1配制的氯化物溶液全部滴加到还原悬浊液中，并同时搅拌； Or add carbon powder to the reducing suspension prepared in step 1 above, and use the separatory funnel to mix the chloride prepared in step 1 at a temperature of -20 ° C ~ 200 ° C for 1min-24h. The entire solution was added dropwise to the reducing suspension, while stirring;

其中上述歩骤 1配制的氯化物溶液中所含阳离子的重量与碳粉的重量比为 10%~70%。 The weight ratio of cations to carbon powder in the chloride solution prepared in step 1 above is 10% to 70%.

3. 分离、洗涤并干燥：将上述步骤 2共还原反应后的混合物过滤；再用乙醇洗涤，直到用硝酸银检测不到滤液中的 C1离子；然后将得到的粉末在真空 O.OlmmHg- lOmmHg下， 50~120°C , 干燥 1~48小时后，得到纳米金属或纳米合金 /碳复合材料，并将该材料保存在惰性环境或真空中。 3. Isolation, washing and drying: filtering the mixture after the co-reduction reaction in step 2 above; washing with ethanol until the C1 ion in the filtrate cannot be detected with silver nitrate; and then the obtained powder is vacuumed O.llmmHg-lOmmHg After drying at 50 ~ 120 ° C for 1 ~ 48 hours, a nano metal or nano alloy / carbon composite material is obtained, and the material is stored in an inert environment or in a vacuum.

本发明所提供的纳米金属或纳米合金 /碳复合材料的制备方法，其中所述的 C1- C4的醇为 C1-C4的直链或支链的一元醇或多元醇，如甲醇、乙醇、乙二醇，异丙醇，丙三醇或丁醇。 The method for preparing a nano-metal or nano-alloy / carbon composite material provided in the present invention, wherein the C1-C4 alcohol is a C1-C4 linear or branched mono- or polyhydric alcohol, such as methanol, ethanol, and ethyl alcohol. Diol, isopropanol, glycerol or butanol.

本发明所提供的纳米金属或纳米合金 /碳复合材料的制备方法，其中在有机溶剂体系中共还原的反应温度应使反应体系保持不凝固，共还原反应优选在 -10-50 C 之间进行。 In the method for preparing a nano-metal or nano-alloy / carbon composite material provided by the present invention, a reaction temperature for co-reduction in an organic solvent system should keep the reaction system from solidifying, and the co-reduction reaction is preferably performed at -10-50 C.

在纳米金属或纳米合金 /碳复合材料的制备过程中，以及在转移和保存纳米金属或纳米合金 /碳复合材料的过程中，纳米金属或纳米合金表面难以避免会发生氧化，因此在所述的纳米金属或纳米合金 /碳复合材料中，一般可检测到氧的存在，氧元素占复合材料中的重量百分比为 0.001%〜10%。 During the preparation of nano-metals or nano-alloys / carbon composites, and during the transfer and storage of nano-metals or nano-alloys / carbon composites, the surface of the nano-metals or nano-alloys is difficult to avoid oxidation, so in the described In nano-metal or nano-alloy / carbon composite materials, the presence of oxygen can generally be detected, and the weight percentage of oxygen element in the composite material is 0.001% to 10%.

此外，本发明的纳米金属或纳米合金 /碳复合材料，还可以通过前面介绍的液相浸渍还原法、气相沉积法或有机金属化合物炭化热解法得到；也可以先通过水热、溶剂热、溶胶凝胶等方法制备出表面沉积金属氧化物的碳复合材料，然后在还原气氛下进行还原的方法制得。这些方法或者成本较高，或者得到的产物不能达到将纳米尺寸的金属或合金均勾沉积分散在碳材料的内外表面的目的。 In addition, the nano-metal or nano-alloy / carbon composite material of the present invention can also be obtained by the liquid phase impregnation reduction method, vapor deposition method, or carbonization pyrolysis method of organometallic compounds described above; it can also be obtained by hydrothermal, solvothermal, A sol-gel method is used to prepare a carbon composite material having a metal oxide deposited on the surface, and then the carbon composite material is reduced in a reducing atmosphere. These methods are either costly, or the products obtained cannot achieve the purpose of depositing and dispersing nano-sized metals or alloys on the inner and outer surfaces of carbon materials.

本发明的纳米金属或纳米合金 /碳复合材料的用途之一是作为二次锤电池的负极活性材料，该负极与含锂的过渡金属氧化物正极、有机电解质溶液、隔膜、电池壳、集流体和引线等组成本发明中的二次锂电池。其中，正极与负极之间 ώ浸泡了有机电解质溶液的隔膜或者聚合物电解质隔开，正极和负极的一端分别在集流体上焯上引线与相互绝缘的电池壳两端相连。 One of the uses of the nanometal or nanoalloy / carbon composite material of the present invention is as a negative electrode active material for a secondary hammer battery, the negative electrode and a lithium-containing transition metal oxide positive electrode, an organic electrolyte solution, a separator, a battery case, and a current collector. And the lead constitute the secondary lithium battery in the present invention. Among them, leaching between the positive electrode and the negative electrode The separator or polymer electrolyte in which the organic electrolyte solution is bubbled is separated, and one end of the positive electrode and the negative electrode is respectively connected with a lead on the current collector and connected to two ends of the battery case which are mutually insulated.

本发明所提供的以纳米金属或纳米合金 /碳复合材料作为二次锂电池的负极活性材料，该负极的制备方法为工业上通用的制备方法，该制备方法包括：（1 ) 将纳米金属或纳米合金 /碳复合材料与导电添加剂混合均匀，再与粘合剂在常温常压下均匀混合制成复合材料浆液。其中导电添加剂指锂离子电池中常用的增加活性物质电导率的物质，如碳黑、乙炔黒、石墨粉、金属粉或金属丝等，其与纳米金属或纳米合金 /碳复合材料的重量百分比为 0%~15%。其中粘合剂包括溶液型的或乳浊液型的粘合剂，例如，将聚四氟乙烯与水混合形成乳浊液型的粘合剂，或将聚偏氟乙烯溶于 N-甲基吡咯垸酮形成溶液型的粘合剂。 In the present invention, a nano metal or a nano alloy / carbon composite material is used as a negative electrode active material of a secondary lithium battery. The preparation method of the negative electrode is a general industrial preparation method, and the preparation method includes: (1) a nano metal or The nano-alloy / carbon composite material is evenly mixed with the conductive additive, and then mixed with the binder at room temperature and pressure to form a composite slurry. The conductive additive refers to a substance commonly used in lithium ion batteries to increase the conductivity of the active material, such as carbon black, acetylene hafnium, graphite powder, metal powder or metal wire, etc., and the weight percentage of the additive with the nano metal or nano alloy / carbon composite material is 0% ~ 15%. Wherein the adhesive includes a solution type or an emulsion type adhesive, for example, polytetrafluoroethylene is mixed with water to form an emulsion type adhesive, or polyvinylidene fluoride is dissolved in N-methyl Pyrrolidone forms a solution-type adhesive.

(2 ) 将上述步骤（1 ) 制成的复合材料浆液均匀地涂敷在作为集流体的各种导电的箔、网、多孔体或纤维体材料上，如铜箔、镍网、泡沬镍或碳毡等载体上，所得薄膜厚度约为 10-150 μιη, 然后将其在 100°C-150°C下烘干，在压力为 l-60Kg/cm² 下压紧，再继续在 100°C-150°C下烘 1-12小时，烘干后粘合剂占薄膜和载体总重量的 2%-15%。按所制备的二次锂电池规格，裁剪成所需要的形状即为负极。 (2) Uniformly apply the composite material slurry prepared in the above step (1) on various conductive foils, meshes, porous bodies or fibrous materials as current collectors, such as copper foil, nickel mesh, and foamed nickel Or carbon felt, the thickness of the obtained film is about 10-150 μm, then it is dried at 100 ° C-150 ° C, compacted at a pressure of 1-60Kg / cm ² and then continued at 100 ° Bake at C-150 ° C for 1-12 hours. After drying, the adhesive accounts for 2% -15% of the total weight of the film and the carrier. According to the specifications of the prepared secondary lithium battery, the negative electrode is cut into a required shape.

用于本发明的二次锂电池的正极活性材料为已知的用于二次锂电池的正极材料，即能可逆地嵌入和脱出锂的含锂的过渡金属氧化物，典型的如锂钴氧化物、锂镍氧化物或锂锰氧化物等。 The positive electrode active material used in the secondary lithium battery of the present invention is a known positive electrode material for a secondary lithium battery, that is, a lithium-containing transition metal oxide capable of reversibly inserting and extracting lithium, such as lithium cobalt oxide. Materials, lithium nickel oxide or lithium manganese oxide.

用于本发明的二次锂电池的有机电解质溶液为二次锂电池通用的电解液，可以由一种有机溶剂或几种有机溶剂组成的混合溶剂中添加一种或几种可溶锂盐组成。典型的有机溶剂例如乙烯碳酸酯、丙烯碳酸酯、二乙基碳酸酯、二甲基碳酸酯、乙基甲基碳酸酯或二甲氧基乙烷等。典型的可溶锂盐如高氯酸锂、四氟硼酸锂、六氟磷酸锂、三氟甲基磺酸锂或六氟砷酸锂等。典型的体系如 1摩尔 /升六氟磷酸锂溶液，所用溶剂为 1:1体积比的乙烯碳酸酯和二乙基碳酸酯的混合溶剂；或 1摩尔 /升的六氟磷酸锂溶液，所用溶剂为 3:7体积比的乙烯碳酸酯和二甲基碳酸酯的混合溶剂。 The organic electrolyte solution used in the secondary lithium battery of the present invention is an electrolyte commonly used in secondary lithium batteries, and may be composed of one organic solvent or a mixed solvent composed of several organic solvents and one or more soluble lithium salts added . Typical organic solvents are, for example, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate or dimethoxyethane. Typical soluble lithium salts are lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate or lithium hexafluoroarsenate. A typical system is a 1 mol / liter lithium hexafluorophosphate solution, and the solvent used is a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1; or a 1 mol / liter lithium hexafluorophosphate solution, the solvent used is 3: 7 volume ratio A mixed solvent of ethylene carbonate and dimethyl carbonate.

用于本发明的二次锂电池的隔膜为二次锂电池通用的隔膜，如多孔聚丙烯隔膜或多孔聚乙烯隔膜等。 The separator used in the secondary lithium battery of the present invention is a separator commonly used in secondary lithium batteries, such as a porous polypropylene separator or a porous polyethylene separator.

本发明的优点在于： The advantages of the invention are:

本发明所提供的纳米金属或纳米合金 /碳复合材料具有良好的稳定性，其纳米金属或纳米合金颗粒不易团聚，在碳表面分散均匀，附着性好，且颗粒尺寸较小。 The nano-metal or nano-alloy / carbon composite material provided by the present invention has good stability. Its nano-metal or nano-alloy particles are not easy to agglomerate, are uniformly dispersed on the carbon surface, have good adhesion, and have a relatively small particle size. small.

本发明所提供的纳米金属或纳米合金 /碳复合材料的制备方法工艺简单，成本低，适于大规模生产，而且制备的纳米金属或纳米合金颗粒尺寸约为 100纳米，它们在碳颗粒的表面分散均匀，与碳材料的附着性好，性能稳定，制备工艺对环境无污染。 The preparation method of the nano-metal or nano-alloy / carbon composite material provided by the present invention has simple process, low cost, and is suitable for large-scale production, and the prepared nano-metal or nano-alloy particles have a size of about 100 nanometers, and they are on the surface of the carbon particles. Evenly dispersed, good adhesion to carbon materials, stable performance, and no environmental pollution caused by the preparation process.

本发明所提供的纳米金属或纳米合金 /碳复合材料，由于碳材料提供了刚性骨架结构，同时纳米金属或纳米合金分散附着在碳材料的内外表面，因而纳米合金不易团聚，稳定性大大提高。特别是当这种复合材料作为二次锂电池的负极材料时，在充放电过程中纳米金属或纳米合金的电化学团聚问题可以大大减轻。而且，在本发明中所用的碳材料及纳米金属或纳米合金材料均为活性的储锂材料，这种复合材料具有很高的储锂容量，使用这种复合材料的二次锂电池具有好的循环特性和安全性，而且动力学上也具有明显的优势。因此，以本发明的纳米金属或纳米合金 /碳复合材料作为负极活性材料的二次锂电池，具有很高的可逆容量，循环性好，安全可靠，耐大电流充放，电极材料廉价，容易制备且对环境友好等显著优点。 Since the nano-metal or nano-alloy / carbon composite material provided by the present invention provides a rigid skeleton structure and the nano-metal or nano-alloy is dispersedly attached to the inner and outer surfaces of the carbon material, the nano-alloy is not easy to agglomerate, and the stability is greatly improved. Especially when such a composite material is used as a negative electrode material of a secondary lithium battery, the problem of electrochemical agglomeration of nano-metals or nano-alloys during charging and discharging can be greatly reduced. Moreover, the carbon materials and nano-metals or nano-alloy materials used in the present invention are active lithium storage materials. This composite material has a high lithium storage capacity, and the secondary lithium battery using this composite material has a good performance. Cyclic characteristics and safety, as well as obvious advantages in dynamics. Therefore, the secondary lithium battery using the nano-metal or nano-alloy / carbon composite material of the present invention as a negative electrode active material has a high reversible capacity, good cycleability, safety and reliability, resistance to large current charge and discharge, cheap electrode materials, and easy Preparation and environmentally friendly and other significant advantages.

以本发明的纳米金属或纳米合金 /碳复合材料作为负极活性材料的二次锂电池，适用于多种场合，例如移动电话、 ^记本电脑、便携式录像机、电子玩具及无绳电动工具等需要可移动电源的场合，特别是较高能量密度的使用场合，如电动汽车、混合动力车、机器人、军事或宇航等领域。 The secondary lithium battery using the nano-metal or nano-alloy / carbon composite material of the present invention as the negative electrode active material is suitable for various applications, such as mobile phones, notebook computers, portable video recorders, electronic toys, and cordless power tools. Mobile power applications, especially applications with higher energy density, such as electric vehicles, hybrid vehicles, robots, military or aerospace.

本发明所提供的纳米金属或纳米合金 /碳复合材料也可用在其它领域，如催化、吸波材料及电子复合材料等。 The nano-metal or nano-alloy / carbon composite materials provided by the present invention can also be used in other fields, such as catalysts, absorbing materials, and electronic composite materials.

附图概述 Overview of the drawings

图 1是本发明实施例 1、 2、 3制备的纳米 Sno.₅Sb。.₅合金 /球形热解硬碳、纳米 Sn ₄₈Sb。₅₂合金 /石墨化中间相碳小球、纳米 Sn^Sb^合金 /针状焦复合材料的 X射线衍射花样； FIG. 1 is a nano Sno. ₅ Sb prepared in Examples 1, 2, and 3 of the present invention. . ₅ alloy / spherical pyrolytic hard carbon, nano Sn ₄₈ Sb. X-ray diffraction pattern of ₅₂ alloy / graphitized mesophase carbon spheres, nano Sn ^ Sb ^ alloy / acicular coke composite;

图 2是本发明实施例 1制备的纳米 Sn。.₅Sb。.₅合金 /球形热解硬碳复合材料的透射电镜照片； FIG. 2 is nano-Sn prepared in Example 1 of the present invention. . ₅ Sb. Transmission electron micrograph of ₅ alloy / spherical pyrolytic hard carbon composite material;

图 3(A)、（B)、（C)分别为本发明实施例 1、 2、 3制备的纳米 S_¾5Sb。.₅合金 /球形热解硬碳、纳米 Sno.₄₈Sb ₅₂合金 /石墨化中间相碳小球、纳米 Sn。.₄Sb_Q.₆合金 /针状焦复合材料的扫描电镜照片； 3 (A), (B), and (C) are nano S _{¾ 5} Sb prepared in Examples 1, 2, and 3 of the present invention, respectively. ₅ alloy / spherical pyrolytic hard carbon, nano Sno. ₄₈ Sb ₅₂ alloy / graphitizable mesophase carbon spheres, nano Sn. Scanning electron micrograph of ₄ Sb _Q. ₆ alloy / needle focal composite;

图 4(A)、（B)分别为釆用本发明实施例 1、 2制备的复合材料作为负极活性材料的锂扣式模拟电池的充放电曲线。 Figures 4 (A) and (B) respectively show that the composite materials prepared in Examples 1 and 2 of the present invention are used as negative electrode active materials. Charge and discharge curve of a lithium button-type analog battery.

具体实施例 Specific embodiment

下面通过实施例对本发明作进一歩的说明。 The present invention is further described below through examples.

实施例 1 Example 1

一. 纳米 Sn。₅Sb。.₅合金 /球形热解硬碳复合材料的制备： I. Nano Sn. ₅ Sb. . Preparation of ₅ alloy / spherical pyrolytic hard carbon composites:

1. 反应液配制： 1. Reaction solution preparation:

( 1 ) 将 1 :1摩尔比的纯度大于 99%的 SbCl^BSnCl₂.2H₂0混合后，溶于乙二醇中形成浓度为 0.5M的 200ml的混合金属氯化物溶液。 (1) SbCl ^ BSnCl ₂ .2H ₂ 0 having a purity of more than 99% in a 1: 1 molar ratio is mixed, and then dissolved in ethylene glycol to form a 200 ml mixed metal chloride solution having a concentration of 0.5M.

(2) 将 15.52g (为将上述（1 ) 的金属氯化物溶液中的金属离子全部还原为 Sn和 Sb 所需化学计量的 95%的量）的 Zn粉（纯度高于 99%，粒度为 lum) 加入到 200ml乙二醇中，搅拌均匀，形成悬浊液。 (2) 15.52 g of Zn powder (amount of 95% of stoichiometry required to reduce all the metal ions in the metal chloride solution (1) to Sn and Sb) (purity higher than 99%, particle size is lum) was added to 200 ml of ethylene glycol and stirred well to form a suspension.

2. 在有机溶剂体系中共还原： 2. Co-reduction in organic solvent systems:

球形热解硬碳材料的制备：将 400克蔗糖溶于 600毫升蒸馏水配制成均相分散体系，加入有机添加剂四乙基氢氧化胺（TEA0H) 使其最终浓度为 1M，搅拌均勾，然后置于容积为 1升的高压釜中并搅拌，转速为 800转 /分钟，填充度为 70%，以 30"C/ 小时的升温速率升温至 200°C，保温 24小时。以 1°C/小时的速率冷却至室温后将产物用蒸馏水洗涤、过滤至滤液透明后，在 120°C下干燥得到中间产物。 Preparation of spherical pyrolytic hard carbon material: 400 g of sucrose is dissolved in 600 ml of distilled water to prepare a homogeneous dispersion system, and the organic additive tetraethylamine hydroxide (TEA0H) is added to make the final concentration of 1M, and the mixture is stirred. Stir in an autoclave with a volume of 1 liter at a speed of 800 rpm and a filling rate of 70%. Increase the temperature to 200 ° C at a temperature rise rate of 30 "C / hour and hold for 24 hours. At 1 ° C / hour After cooling to room temperature, the product was washed with distilled water, filtered until the filtrate was transparent, and then dried at 120 ° C to obtain an intermediate product.

然后将该中间产物放在管式炉（炉管长 1000mm, 直径 60隱）中，在氮气保护下，以 300 "C/小时的速率升温至 1000 ，氮气流量为 25ml/min，恒温 6小时后以 20"C/ 小时的速率冷却至室温，所得到的粉料即为最终的球形热解硬碳产物，表示为 HCSlO o BET测量比表面积为 400m²/g，其中外表面积为 50 m²/g，微孔表面积为 350m²/g；用 X-射线衍射（XRD ) 方法测得平均孔径为 lnm， d₀₀₂=0.392nm , La=4.9nm, Lc=2.8nm, 粒径在 ΙΟμπι左右。 The intermediate product was then placed in a tube furnace (furnace tube length 1000 mm, diameter 60 hidden), and heated to 1000 at a rate of 300 "C / hour under nitrogen protection, with a nitrogen flow rate of 25 ml / min, after a constant temperature of 6 hours Cool to room temperature at a rate of 20 "C / hour. The resulting powder is the final spherical pyrolytic hard carbon product, expressed as HCSlO o BET specific surface area of 400 m ² / g, where the external surface area is 50 m ² / g, the microporous surface area is 350 m ² / g; the average pore diameter measured by X-ray diffraction (XRD) method is 1 nm, d ₀₀₂ = 0.392 nm, La = 4.9 nm, Lc = 2.8 nm, and the particle diameter is about 10 μm.

在有机溶剂体系中共还原：将平均粒度为 lOum的球形热解硬碳 72g加入到上述歩骤 1配制的金属氯化物溶液中，搅拌均匀。在 0.0~5.0°C的温度下，在 1小时内，用分液漏斗将 Zn粉还原悬浊液缓慢滴加到含有 HCS10的金属氯化物溶液中，并同时高速搅拌。 Co-reduction in an organic solvent system: 72 g of spherical pyrolytic hard carbon having an average particle size of 10 um was added to the metal chloride solution prepared in step 1 above, and stirred well. At a temperature of 0.0 ~ 5.0 ° C, within 1 hour, the Zn powder reduction suspension was slowly added dropwise to the metal chloride solution containing HCS10 using a separatory funnel, and simultaneously stirred at high speed.

3. 分离、洗涤、干燥： 3. Separation, washing and drying:

将歩骤 2所得到的黑色产物过滤后，用乙醇清洗，直到用硝酸银检测不到滤液中的 Cl_离子，然后将得到的粉末在真空 O.lmmHg下， 80。C干燥 5小时后，即得到纳米 Sn。.₅Sb。₅合金 /HCS 10复合材料样品。二. 纳米 S_¾5Sb。.₅合金 /球形热解硬碳复合材料性能测试与分析： The black product obtained in step 2 was filtered and washed with ethanol until no Cl_ ions were detected in the filtrate with silver nitrate, and then the obtained powder was vacuumed at 0.1 mmHg, 80. After C was dried for 5 hours, nano-Sn was obtained. . ₅ Sb. ₅ alloy / HCS 10 composite samples. 2. Nano S _{¾ 5} Sb. . Performance test and analysis of ₅ alloy / spherical pyrolytic hard carbon composite material:

根据常规化学分析的结果，纳米 S ₅Sb ₅合金 /HCS10复合材料中纳米 Sn。.₅Sb。.₅ 合金占复合材料的重量百分比为 25%。纳米 Sn。.₅Sb。.₅合金 /HCS10复合材料的 X射线衍射花样如图 1中 A所示，该结果表明沉积在 HCS10上的纳米 Sn。.₅Sb。.₅合金为纯相的 β-SnSb合金，根据谢乐公式计算，其晶粒尺寸为 25nm。纳米 Sn。₅Sb。.₅合金 /HCS10 复合材料扫描电镜照片为图 3(A), 图 3(A)中 a图放大倍数为 6000倍，标尺为 3um_; b 图放大倍数为 50000倍，标尺为 360nm; 该结果说明 99%以上的纳米合金沉积在 HCS10颗粒表面，且分布均匀，合金颗粒平均尺寸为 110nm。电子能量分布 X光吸收光谱 (EDAX)结果显示，复合材料中氧占该复合材料总重量的百分比为 0.5%， ώ 此推算出碳占复合材料的重量百分比为 74.5%。该复合材料的透射电镜照片参见图 2，说明合金颗粒与碳表面直接接触，且部分合金渗入到孔结构中，这样保证了纳米合金与碳材料的紧密接触。 BET方法测量纳米 Sno.₅Sb。.₅/HCS10复合材料的微孔比表面积为 150m²/g，微孔体积比原料球形热解硬碳材料减少了 60%, 计算表明，孔内的合金占纳米合金的总量百分比为 18%。由于 HCS10内部微孔的平均孔径为 2nm，孔分布从 lnm到 10nm，因此孔内的合金颗粒尺寸为 1-10nm。 According to the results of conventional chemical analysis, nano Sn in the nano S ₅ Sb ₅ alloy / HCS10 composite. . ₅ Sb. ₅ alloys account for 25% by weight of the composite. Nano Sn. . ₅ Sb. The X-ray diffraction pattern of the ₅ alloy / HCS10 composite is shown in Fig. 1A. The results show that the nano-Sn deposited on the HCS10. . ₅ Sb. ₅ alloy is a pure phase of β-SnSb alloy, and its grain size is 25nm according to the calculation of Shelley's formula. Nano Sn. ₅ Sb. The scanning electron microscope photograph of the ₅ alloy / HCS10 composite material is shown in Figure 3 (A), in Figure 3 (A), the magnification of a is 6000 times and the scale is 3um _{; the} magnification of b is 50,000 times, and the scale is 360nm; More than 99% of the nano-alloys are deposited on the surface of HCS10 particles and are evenly distributed. The average size of the alloy particles is 110 nm. Electron energy distribution X-ray absorption spectroscopy (EDAX) results show that oxygen in the composite material accounts for 0.5% of the total weight of the composite material, and it is inferred that carbon accounts for 74.5% of the weight of the composite material. The transmission electron microscope photograph of the composite material is shown in FIG. 2, which shows that the alloy particles are in direct contact with the carbon surface, and part of the alloy penetrates into the pore structure, which ensures close contact between the nano-alloy and the carbon material. The BET method measures nano Sno. ₅ Sb. The ₅ / HCS10 composite has a micropore specific surface area of 150m ² / g, and the micropore volume is reduced by 60% compared to the raw spherical pyrolytic hard carbon material. Calculations show that the alloy in the pores accounts for 18% of the total amount of the nano-alloy. . Since the average pore diameter of the micropores in the HCS10 is 2 nm, and the pore distribution is from 1 nm to 10 nm, the alloy particle size in the pores is 1-10 nm.

三. 纳米 Sn。.₅Sb。.₅合金 /球形热解硬碳复合材料的应用： Three. Nano Sn. . ₅ Sb. . Application of ₅ alloy / spherical pyrolytic hard carbon composites:

纳米 S_¾5Sb。.₅合金 /HCS10复合材料作为二次锂电池的负极活性材料的应用，该电极的制备方法与锂离子电池工业所用制备方法相似，歩骤如下：将上述制备的纳米合金 /碳复合材料，与粘结剂聚偏氟乙烯的 N-甲基吡咯烷酮溶液在常温常压下混合形成浆料，均匀涂敷于作为集流体的铜箔衬底上，所得薄膜厚度约 ΙΟΟμηι。将得到的薄膜在 150°C下烘干后，在 20Kg/cm²下压紧，然后继续在 150°C下烘干 12 小时。烘干后，复合材料与聚偏氟乙烯的重量百分比为 95: 5。然后将薄膜裁剪为直径为 1.6cm的圆形薄片，作为纳米合金 /碳复合材料电极，为了考察其作为二次锂电池负极活性材料的电化学性能，根据通用的研究方法，采用一个常规的两电极实验扣式电池 2016型来进行研究。该实验电池中，电解液为 1摩尔 /升的六氟磷酸锂 (LiPF₆)溶液，该溶液所用溶剂为 1： 1体积比的乙烯碳酸酯 (EC)和二乙基碳酸酯 (DEC) 的混合溶剂；隔膜为多孔聚丙烯隔膜 Celgard 300_; 直径为 1.8cm，厚 lmm的金属锂片作为对电极。在充氩手套箱中（H₂0<5ppm, 0₂<5ppm) ，组装成实验电池。实验电池由受计算机控制的自动充放电仪进行充放电循环测试。电流密度为 O.lmA/cm² , 充电截止电压为 2.0V, 放电截止电压为 0.00V。充放电曲线参见图 4(A), 从该曲线可以看出，该复合材料可逆容量为 500mAh/g，远高于目前商业二次锂电池中碳材料的可逆容量 (330mAh/g)，电池的循环性较好，充放电曲线的形状为典型的纳米 Sn。.₅Sb。.₅合金 /球形热解硬碳复合材料的充放电曲线，适合于动力电池的要求。第一周充放电效率为 84%，第十周充放电效率为 99%。这两个参数反映了库仑效率和循环性，列在表 1中。 Nano S _{¾ 5} Sb. . Application of ₅ alloy / HCS10 composite material as the negative electrode active material of secondary lithium battery. The preparation method of the electrode is similar to that used in the lithium ion battery industry. The steps are as follows: The nano alloy / carbon composite material prepared above is combined with The N-methylpyrrolidone solution of the binder polyvinylidene fluoride is mixed at normal temperature and pressure to form a slurry, and the slurry is uniformly coated on a copper foil substrate as a current collector. After the obtained film was dried at 150 ° C, it was compacted at 20Kg / cm ² , and then dried at 150 ° C for 12 hours. After drying, the weight percentage of the composite material and polyvinylidene fluoride is 95: 5. The film was then cut into a round sheet with a diameter of 1.6 cm as a nano-alloy / carbon composite electrode. In order to investigate its electrochemical performance as a negative electrode active material for secondary lithium batteries, a conventional The electrode experiment button battery 2016 type was studied. In this experimental battery, the electrolyte is a 1 mol / liter lithium hexafluorophosphate (LiPF ₆ ) solution, and the solvent used in the solution is a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1: 1; The separator was a porous polypropylene separator Celgard 300 _; a metal lithium sheet with a diameter of 1.8 cm and a thickness of 1 mm was used as a counter electrode. An argon-filled glove box (H ₂ 0 <5ppm, 0 ₂ <5ppm) was assembled into an experimental battery. The experimental battery was charged and discharged by a computer-controlled automatic charge-discharge meter. The current density is O.lmA / cm ² , the charge cut-off voltage is 2.0V, and the discharge cut-off voltage is 0.00V. The charge-discharge curve is shown in Figure 4 (A). From this curve, it can be seen that the reversible capacity of the composite material is 500mAh / g, which is much higher than the current commercial two. The reversible capacity of the carbon material in the lithium secondary battery (330mAh / g), the battery has good cycle performance, and the shape of the charge-discharge curve is a typical nano-Sn. . ₅ Sb. . Charging and discharging curve of ₅ alloy / spherical pyrolytic hard carbon composite material, suitable for power battery requirements. The charge and discharge efficiency in the first week was 84%, and the charge and discharge efficiency in the tenth week was 99%. These two parameters reflect Coulomb efficiency and cyclicity and are listed in Table 1.

实施例 2 Example 2

一. 纳米 Sn。₄₈Sb。.₅₂合金 /石墨化中间相碳小球复合材料的制备-I. Nano Sn. ₄₈ Sb. . Preparation of ₅₂ alloy / graphitized mesophase carbon pellet composite-

1. 反应液配制： 1. Reaction solution preparation:

( 1 ) 将 1:1摩尔比的 SbCl^BSnCl₂.2H₂0混合后，溶于丙三醇中形成浓度为 0.2M的 400ml的混合金属氯化物溶液。 (1) A 1: 1 molar ratio SbCl ^ BSnCl _₂ .2H ₂ 0 After mixing, glycerol was dissolved in a concentration of 0.2M mixed metal chloride solution in the 400ml.

(2) 将 13.08g (为将上述（1 ) 的金属氯化物溶液中的金属离子全部还原为 Sn和 Sb 所需化学计量的 100%的量）的超细 Zn粉 (粒度为 lOOnm, 纯度为 99%)加入到 200ml 丙三醇中，搅拌均匀，形成悬浊液。 ' (2) 13.08 g (an amount of 100% of the stoichiometric amount required to reduce all the metal ions in the metal chloride solution of (1) above to Sn and Sb) (a particle size of 100 nm and a purity of 100%) (99%) was added to 200 ml of glycerol, and stirred well to form a suspension. '

石墨化中间相碳小球记为 CMS28 , 由鞍山热能院制造，平均粒度为 15um， XRD测量其 (1。。₂为0.3351^1， La、 Lc>100nm。 BET测量其比表面积为 lm²/g，基本没有微孔。 The graphitized mesophase carbon spheres are denoted as CMS28, manufactured by Anshan Thermal Energy Institute, with an average particle size of 15um, which is measured by XRD (1 ... ₂ is 0.3351 ^ 1, La, Lc> 100nm. The specific surface area measured by BET is lm ² / g, There are almost no micropores.

在室温 25°C下，将 45.8g CMS28加入到上述步骤 1配制的 Zn粉还原悬浊液中，搅拌均匀，形成碳粉和 Zn粉的混合悬浊液。在 2小时内，用分液漏斗将金属氯化物溶液缓慢滴加到碳粉和 Zn粉的混合悬浊液中，并同时高速搅拌。 At room temperature of 25 ° C, 45.8 g of CMS28 was added to the Zn powder reduction suspension prepared in step 1 above, and stirred well to form a mixed suspension of carbon powder and Zn powder. Within 2 hours, the metal chloride solution was slowly added dropwise to a mixed suspension of carbon powder and Zn powder using a separatory funnel, while stirring at high speed.

3. 分离、洗涤、干燥： 3. Separation, washing and drying:

将歩骤 2所得到的黑色产物过滤后，用乙醇清洗，直到用硝酸银检测不到滤液中的 CI-离子，然后将得到的粉末在真空 O.OlmmHg下， 120^DC干燥 12小时后，即得到纳米 Sn。.₄₈Sb。.₅₂合金 /CMS28复合材料样品。 The black ho step 2 product obtained after filtration, washed with ethanol, until the CI- ion not detected with silver nitrate in the filtrate, and the resulting powder under vacuum O.OlmmHg, 120 ^D C dried for 12 hours, That is, nano Sn was obtained. ₄₈ Sb. ₅₂ alloy / CMS28 composite samples.

二. 纳米 Sn。₄₈Sb。.₅₂合金 /石墨化中间相碳小球复合材料性能测试与分析： 2. Nano Sn. ₄₈ Sb. . Performance test and analysis of ₅₂ alloy / graphitized mesophase carbon pellet composites:

根据常规化学分析的结果，纳米 Sn_Q.₄₈Sb。.₅₂合金 /CMS28复合材料中纳米 S ₄₈Sb。.₅₂合金占复合材料的重量百分比为 29.5%。该复合材料的 X射线衍射花样如图 1中 B所示，该结果表明沉积在 CMS28上的合金为纯相的 β-SnSb合金，根据谢乐公式 (Scherrer)计算，其晶粒尺寸为 34nm。该复合材料扫描电镜照片为图 3(B)，其中 a图标尺为 100um， b图标尺为 lOOnm, 该结果说明 90%以上的纳米合金沉积在 CMS28颗粒表面，且分布均勾，合金颗粒平均尺寸为 100nm。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 0.2%，由此推算出 CMS28占复合材料的重量百分比为 70.3%。 Based on the results of conventional chemical analysis, nano-Sn _Q. ₄₈ Sb. Nano S ₄₈ Sb in ₅₂ alloy / CMS28 composite. The weight percentage of ₅₂ alloy to the composite material is 29.5%. The X-ray diffraction pattern of the composite material is shown as B in FIG. 1. The result indicates that the alloy deposited on the CMS28 is a pure phase β-SnSb alloy. According to Scherrer's formula, the grain size is 34 nm. The composite scanning electron microscope photograph is shown in Figure 3 (B), where the a scale is 100um and the b scale is 100nm. The results show that more than 90% of the nano-alloys are deposited on the surface of the CMS28 particles, and the distribution is uniform. The average size of the alloy particles 100nm. The EDAX results show that the weight percentage of oxygen in the composite material is 0.2%, and the CMS28 accounted for The weight percentage is 70.3%.

三. 纳米 Sn。.₄₈Sb。₅₂合金 /石墨化中间相碳小球复合材料的应用： Three. Nano Sn. ₄₈ Sb. _{Application of 52} alloy / graphitized mesophase carbon pellet composites:

采用实施例 1相同的方法，将纳米 Sno.₄₈Sb。.₅₂合金 /CMS28复合材料制备成电极，并采用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1 相同的测试方法进行测试，其充放电曲线如图 4(B)所示，此充放电曲线为典型的纳米 Sn。.₄₈Sb ₅₂合金 /石墨类碳的充放电曲线，其可逆容量为 450mAh/g，循环性较好。电化学性能参数示于表 1。 ₄₈ Sb。 Using the same method as in Example 1, the nano Sno. ₄₈ Sb. ₅₂ alloy / CMS28 composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 type described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery, as assembled in Example 1. Into an experimental battery. The test is performed by using the same test method as in Example 1. The charge-discharge curve is shown in FIG. 4 (B), and the charge-discharge curve is a typical nano-Sn. The charge and discharge curve of ₄₈ Sb ₅₂ alloy / graphite-based carbon has a reversible capacity of 450 mAh / g and good cycleability. The electrochemical performance parameters are shown in Table 1.

实施例 3 Example 3

按照实施例 2所述的制备方法，制备纳米 S_¾4Sb。.₆合金 /石油焦复合材料。所不同之处在于：歩骤 1中所用醇为乙醇。歩骤 2所用原料碳粉为针状石油焦，记为 coke, 由中国鞍山沿海化工厂提供，平均粒度为 50um， XRD测量其 d_Q。₂为 0.35nm， Lc为 5nm， BET测量其比表面积为 4m²/g，不含微孔。步骤 3在真空 ImmHg下， 50°C 干燥 12小时后，得到该复合材料。 According to the preparation method described in Example 2, nano S _{¾ 4} Sb was prepared. . ₆ alloy / petroleum coke composite. The difference is that the alcohol used in step 1 is ethanol. The raw material carbon powder used in step 2 is acicular petroleum coke, denoted as coke, provided by Anshan Coastal Chemical Plant, China, with an average particle size of 50um, and its d _{Q is} measured by XRD. ₂ is 0.35 nm, Lc is 5 nm, and its specific surface area is 4 m ² / g as measured by BET, and it does not contain micropores. In step 3, the composite material is obtained after drying at 50 ° C. for 12 hours under a vacuum of 1 mmHg.

根据常规化学分析的结果，纳米 S_n。.₄Sb ₆合金 /石油焦复合材料中纳米 Sn ₄Sb ₆ 合金占该复合材料总重量的百分比为 30.1%。该复合材料的 X射线衍射花样如图 1中 C所示，该结果表明沉积在石油焦上的合金为纯相的 β-SnSb合金，根据谢乐公式计算，其晶粒尺寸为 36nm。该复合材料扫描电镜照片为图 3(C)，其中 a图标尺为 50um, b图标尺为 lum，结果说明 80%以上的纳米合金沉积在石油焦颗粒表面，合金颗粒平均尺寸为 150nm。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 5%。 The results of chemical analysis of a conventional nano S _n. The percentage of nano-Sn ₄ Sb ₆ alloy in the ₄ Sb ₆ alloy / petroleum coke composite material to the total weight of the composite material is 30.1%. The X-ray diffraction pattern of the composite material is shown as C in FIG. 1. The result indicates that the alloy deposited on petroleum coke is a pure phase β-SnSb alloy, and its grain size is 36 nm according to the calculation of Xie Le formula. The scanning electron microscope photograph of the composite material is shown in FIG. 3 (C), where the a scale is 50um and the b scale is lum. The results show that more than 80% of the nano-alloys are deposited on the surface of petroleum coke particles, and the average size of the alloy particles is 150 nm. The EDAX results show that the weight percentage of oxygen in the composite material is 5%.

采用实施例 1相同的方法，将该复合材料制备成电极，并釆用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1相同的测试方法进行测试，其可逆容量为 330mAh/g，循环性较好。电化学性能参数示于表 1中。另外，该模拟电池大电流（1C) 放电仍然能保持 90%的可逆容量。 In the same manner as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Assembled into an experimental battery as in Example 1. The test was performed using the same test method as in Example 1. The reversible capacity was 330 mAh / g, and the cycle was good. The electrochemical performance parameters are shown in Table 1. In addition, the high-current (1C) discharge of the analog battery can still maintain 90% of the reversible capacity.

实施例 4 Example 4

按照实施例 1所述的制备方法，制备纳米 Ino.₅Sb。.₅合金 /HCS10E复合材料。所不同之处在于：歩骤 1中 SnCl₂.2H₂0替换为 InCl_{3 ;} 还原剂替换为超细 Fe粉 (粒度为 50nm) , 其用量为所需化学计量的 90%。步骤 2中所用原料碳粉为 HCS10E , HCS10E为经过 C0₂和水蒸汽扩孔的 HCS10， BET测量 HCS10E比表面积为 3000m²/g, 其中外表面积为 50m²/g，微孔表面积 2950m²/g; XRD方法测得平均孔径为 2nm， d₀₀₂=0.410nm, La=1.5nm, Lc=1.3nm_; 碳粉的加入量为 60g。 ₅ Sb。 According to the preparation method described in Example 1, nano Ino. ₅ Sb. . ₅ alloy / HCS10E composite. The differences are as follows: In step 1, SnCl ₂ .2H ₂ 0 is replaced with InCl _{3; the} reducing agent is replaced with ultra-fine Fe powder (particle size is 50 nm), and the amount is 90% of the required stoichiometry. The raw material carbon powder used in step 2 is HCS10E, HCS10E is HCS10 after C0 ₂ and water vapor reaming. The specific surface area of HCS10E measured by BET is 3000m ² / g, where the external surface area is 50m ² / g, and the microporous surface area is 2950m ² / g; the average pore diameter measured by XRD method is 2nm, d ₀₀₂ = 0.410nm, La = 1.5nm, Lc = 1.3nm _; The amount added was 60 g.

根据常规化学分析的结果，纳米 In。.₅Sb。.₅合金/ HCS 10E复合材料中纳米 In。.₅Sb。.₅ 合金占该复合材料的重量百分比为 40%。根据扫描电镜实验结果，沉积在 HCS10E 外表面上合金的平均颗粒尺寸为 90nm，游离的合金占合金总重量的百分比为 0.1%。根据 BET测定的微孔体积变化及合金密度计算， HCS10E外表面上的合金占合金总重量的 49.9%，内表面上的合金占合金总重量的 50%，填充孔内的合金尺寸从 lnm到 50nm。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 2%。 According to the results of conventional chemical analysis, nanometer In. . ₅ Sb. . Nano-In in ₅ alloy / HCS 10E composites. . ₅ Sb. ₅ alloy accounts for 40% by weight of the composite material. According to the results of SEM experiments, the average particle size of the alloy deposited on the outer surface of HCS10E was 90 nm, and the percentage of free alloy to the total weight of the alloy was 0.1%. Based on the pore volume change and alloy density calculated by BET, the alloy on the outer surface of HCS10E accounts for 49.9% of the total weight of the alloy, the alloy on the inner surface accounts for 50% of the total weight of the alloy, and the size of the alloy in the filled hole ranges from 1nm to 50nm . The EDAX results show that the weight percentage of oxygen in the composite material is 2%.

采用实施例 1相同的方法，将复合材料制备成电极，并釆用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1相同的测试方法进行测试，实验数据示于表 1中。 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. An experimental battery was assembled as in Example 1. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.

实施例 5 Example 5

按照实施例 2所述的制备方法，制备纳米 Zn_fl.₅Sb_{fl 5}合金 /HCS10复合材料。所不同之处在于：歩骤 1中的原料 SnCl₂.2H₂0替换为 ZnCl₂，所用溶剂为异丙醇，氯化物溶液体积为 8升，氯化物溶液中 8½¾与2!^1₂的浓度为 0.01M; 步骤 1中的还原剂替换为 Mg粉 (粒度为 10um)，其用量为所需化学计量的 90%，配制成 40ml的 Mg粉异丙醇悬浊液。歩骤 2中所用原料碳粉为 HCS10, 加入量为 16.5g; 在共还原反应过程中，滴加时间为 24小时，反应温度为 -10°C。歩骤 3在真空 O.lmmHg下， 120 干燥 48小时后得到该复合材料。 According to the preparation method described in Example 2, a nano-Zn _fl . ₅ Sb _{fl 5} alloy / HCS10 composite material was prepared. The differences are as follows: The raw material SnCl ₂ .2H ₂ 0 in step 1 is replaced by ZnCl ₂ , the solvent used is isopropanol, the volume of the chloride solution is 8 liters, and 8½¾ and 2! ^ 1 ₂ in the chloride solution The concentration is 0.01M; the reducing agent in step 1 is replaced with Mg powder (particle size is 10um), the amount of which is 90% of the required stoichiometry, and is formulated into a 40ml Mg powder isopropanol suspension. The raw material carbon powder used in step 2 is HCS10, and the added amount is 16.5g; during the co-reduction reaction, the dropping time is 24 hours, and the reaction temperature is -10 ° C. In step 3, the composite material was obtained after drying at 120 ° C for 48 hours under a vacuum of 0.1 mmHg.

根据常规化学分析的结果，纳米 Z_¾5Sb。.₅合金 /HCS10复合材料中纳米 Zn^Sb^ 合金占复合材料总重量的百分比为 70%。根据扫描电镜实验结果，沉积在 HCS10外表面上合金的平均颗粒尺寸为 250nm，游离的合金占合金总重量的比例为 30%。根据 BET测定的微孔体积变化及合金密度计算， HCS10外表面上的合金占合金总重量的比例为 65%，内表面上的合金占合金总重量的比例为 5%，填充孔内的合金尺寸从 1到 10mn。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 3%。 According to the results of conventional chemical analysis, nanometer Z _{¾ 5} Sb. The percentage of nano-Zn ^ Sb ^ alloy in the ₅ alloy / HCS10 composite material is 70% of the total weight of the composite material. According to the scanning electron microscope experiment results, the average particle size of the alloy deposited on the outer surface of HCS10 was 250 nm, and the proportion of free alloy to the total weight of the alloy was 30%. Based on the pore volume change and alloy density calculated by BET, the proportion of the alloy on the outer surface of HCS10 to the total alloy weight is 65%, the proportion of the alloy on the inner surface to the total alloy weight is 5%, and the alloy size in the filled hole From 1 to 10mn. EDAX results show that the weight percentage of oxygen in the composite material is 3%.

采用实施例 1相同的方法，将复合材料制备成电极，并采用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1相同的测试方法进行测试，实验数据示于表 1中。实施例 6 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1. Example 6

按照实施例 2所述的制备方法，制备纳米 Sb/HCS10复合材料。所不同之处在于：歩骤 1中所配制的金属氯化物溶液为 30ml 3M的 SbCl₃甲醇溶液；配制 2升的 Zn 粉甲醇悬浊液， Zn粉的加入量为 8.7g。步骤 2中所用原料碳粉为 HCS10，碳粉的加入量 23g; 在共还原反应过程中，滴加时间为 1分钟，反应温度为 -20°C。步骤 3在真空 O.OlmmHg下， 50°C干燥 1小时后，得到该复合材料。 According to the preparation method described in Example 2, a nano Sb / HCS10 composite material is prepared. The difference is that: The metal chloride solution prepared in step 1 is 30 ml of 3M SbCl ₃ methanol solution; 2 liters of Zn powder methanol suspension is prepared, and the amount of Zn powder added is 8.7 g. The raw material carbon powder used in step 2 is HCS10, and the added amount of the carbon powder is 23g; during the co-reduction reaction, the dropping time is 1 minute, and the reaction temperature is -20 ° C. In step 3, the composite material is obtained after drying at 50 ° C. for 1 hour under a vacuum of 0.1 mmHg.

根据常规化学分析的结果，纳米 Sb/HCS10复合材料中纳米 Sb占该复合材料总重量的百分比为 30%。根据扫描电镜实验结果，沉积在 HCS10外表面上金属 Sb的平均颗粒尺寸为 120nm，游离的 Sb占金属 Sb总重量的比例为 5%。根据 BET测定的微孔体积变化及合金密度计算，外表面上的 Sb占金属 Sb总重量的比例为 90%, 内表面上的 Sb占金属 Sb总重量的比例为 5%，填充孔内的金属尺寸从 l-10nm。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 4%。 According to the results of conventional chemical analysis, the percentage of nano-Sb in the total weight of the nano-Sb / HCS10 composite is 30%. According to the results of SEM experiments, the average particle size of metal Sb deposited on the outer surface of HCS10 was 120 nm, and the proportion of free Sb to the total weight of metal Sb was 5%. According to the pore volume change and alloy density calculated by BET, the proportion of Sb on the outer surface to the total weight of metal Sb is 90%, and the proportion of Sb on the inner surface to the total weight of metal Sb is 5%. Sizes range from l-10nm. The EDAX results show that the weight percentage of oxygen in the composite material is 4%.

采用实施例 1相同的方法，将复合材料制备成电极，并采用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1相同的测试方法进行测试，电化学性能参数示于表 1中。 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The electrochemical performance parameters are shown in Table 1.

实施例 7 Example 7

按照实施例 1所述的制备方法，制备纳米 Sn。₆C_{U 4}合金 /CMS28复合材料。所不同之处在于：歩骤 1中的原料 SbCl₃替换为 CuCl₂，所用醇为丁醇，所配制的混合金属氯化物溶液中 SnCl₂的浓度为 0.6M, 010₂的浓度为 0.4M; 所用还原剂为超细 Zn 粉 (粒度为 20nm)，其用量为所需化学计量的 97%。步骤 2中所用原料碳粉为粒度为 lum的 CMS28。 According to the preparation method described in Example 1, nano-Sn was prepared. ₆ C _{U 4} alloy / CMS28 composite. The difference is that: the raw material SbCl ₃ in step 1 is replaced with CuCl ₂ , the alcohol used is butanol, and the concentration of SnCl ₂ in the prepared mixed metal chloride solution is 0.6M, and the concentration of 010 ₂ is 0.4M; The reducing agent used is ultra-fine Zn powder (particle size is 20nm), and its amount is 97% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of lum.

根据常规化学分析的结果，纳米 Sno.₆Cuo.₄合金 /CMS28复合材料中纳米 Sn。.₆Cu。.₄合金占该复合材料总重量的百分比为 20%。根据扫描电镜实验结果，沉积在 CMS28外表面上合金的平均颗粒尺寸为 150nm，游离的合金占合金总重量的比例为 15%。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 0.5%。 According to the results of conventional chemical analysis, nano-Sn. ₆ Cuo. ₄ alloy / CMS28 composites. . ₆ Cu. The percentage of ₄ alloy to the total weight of the composite is 20%. According to the results of SEM experiments, the average particle size of the alloy deposited on the outer surface of CMS28 was 150 nm, and the proportion of free alloy to the total weight of the alloy was 15%. The EDAX results show that the weight percentage of oxygen in the composite material is 0.5%.

采用实施例 1相同的方法，将复合材料制备成电极，并采用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1相同的测试方法进行测试，实验数据示于表 1中。 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.

实施例 8 按照实施例 1所述的制备方法，制备纳米8 ₄81₎。.₅₍^¾。₄合金/0^28复合材料。所不同之处在于：步骤 1中所用还原剂为超细 Zn粉 (粒度为 20nm)，其用量为所需化学计量的 105%。歩骤 2中所用原料碳粉为粒度为 50um的 CMS28。 Example 8 According to the preparation method described in Example 1, nano 8 ₄ 81 _{) is} prepared. _{5 (} ^ ¾. ₄ alloy / 0 ^ 28 composite material. The difference is that: The reducing agent used in step 1 is ultra-fine Zn powder (grain size 20nm), and the amount is 105% of the required stoichiometry. 歩The raw material carbon powder used in step 2 was CMS28 with a particle size of 50um.

根据常规化学分析的结果，纳米 311₀.₄31>。.₅₆211₍₎.。₄合金/0^828复合材料中纳米 Sn₀.₄Sb₀.₅₆Zn₀.₀₄合金占该复合材料总重量的百分比为 35%，合金的颗粒尺寸为 lOOnm, 游离的合金占合金总重量比例为 5%，该复合材料中氧占复合材料的重量百分比为 0.001%。 According to the results of conventional chemical analysis, nano 311 _0. ₄ 31>. . ₅₆ 211 ₍₎ ... The percentage of nano Sn _0. ₄ Sb _0. ₅₆ Zn _0. ₀₄ alloy in the ₄ alloy / 0 ^ 828 composite material is 35% of the total weight of the composite material, the particle size of the alloy is 100 nm, and the ratio of the free alloy to the total weight of the alloy is It is 5%, and the weight percentage of oxygen in the composite material is 0.001%.

采用实施例 1相同的方法，将复合材料制备成电极，并采用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。釆用如实施例 1相同的测试方法进行测试，实验数据示于表 1中。 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery.测试 The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.

实施例 9 Example 9

按照实施例 1所述的制备方法，制备纳米 Sn/HCS10E复合材料。所不同之处在于：歩骤 1中的金属氯化物原料不含 SbCl₃。步骤 2中所用原料碳粉为 HCS10E, 碳粉的加入量为 16.5g，共还原反应温度为 -10°C。 According to the preparation method described in Example 1, a nano-Sn / HCS10E composite material is prepared. The difference is that the metal chloride raw material in step 1 does not contain SbCl ₃ . The raw material carbon powder used in step 2 is HCS10E, the amount of carbon powder added is 16.5 g, and the total reduction reaction temperature is -10 ° C.

根据常规化学分析的结果，纳米 Sn/HCS10E复合材料中纳米 Sn占该复合材料总重量百分比为 60%。根据扫描电镜实验结果，沉积在 HCS10E外表面上 Sn的平均颗粒尺寸为 250nm，游离的 Sn占金属 Sn总重量的百分比为 15%。根据 BET测定的微孔体积变化及合金密度计算，外表面上的 Sn占金属 Sn总重量的百分比为 50%，内表面上的 Sn占金属 Sn总重量的百分比为 35%，填充孔内的金属尺寸从 lnm到 50nm。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 0.5%。 According to the results of conventional chemical analysis, nano-Sn / HCS10E composites account for 60% of the total weight of the composite by nano-Sn. According to SEM experiment results, the average particle size of Sn deposited on the outer surface of HCS10E was 250 nm, and the percentage of free Sn to the total weight of metal Sn was 15%. According to the pore volume change and alloy density calculated by BET, the percentage of Sn on the outer surface to the total weight of metal Sn is 50%, and the percentage of Sn on the inner surface to the total weight of metal Sn is 35%. Sizes range from 1 nm to 50 nm. The EDAX results show that the weight percentage of oxygen in the composite material is 0.5%.

采用实施例 1相同的方法，将复合材料制备成电极，并釆用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。釆用如实施例 1相同的测试方法进行测试，实验数据示于表 1中。 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. An experimental battery was assembled as in Example 1.测试 The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.

实施例 10 Example 10

按照实施例 1所述的制备方法，制备纳米 In/HCS10E复合材料。所不同之处在于：歩骤 1中的余属氯化物溶液为 InCl₃的异丙醇溶液；步骤 2中所用原料碳粉为平均直径 lOOnm的球形热解硬碳 HCS10E, 碳粉的加入量为 34g，共还原反应温度为- 20^oC。 According to the preparation method described in Example 1, a nano In / HCS10E composite material is prepared. The difference is that the remaining chloride solution in step 1 is an isopropyl alcohol solution of InCl ₃ ; the raw material carbon powder used in step 2 is a spherical pyrolytic hard carbon HCS10E with an average diameter of 100 nm, and the amount of carbon powder added is 34g, co-reduction reaction temperature is -20 ^o C.

根据常规化学分析的结果，纳米 In/HCS10E复合材料中纳米 In占该复合材料总重量的百分比为 30%。根据扫描电镜实验结果，沉积在 HCS10E外表面上 In的平均颗粒尺寸为 10nm，游离的 In占金属 In总重量的百分比为 5%。根据 BET测定的微孔体积变化及合金密度计算，外表面上的 In占金属 In总重量的百分比为 60%，内表面上的 In占金属 In总重量的百分比为 35%，填充孔内的金属尺寸从 lnm到 5nm。 EDAX 结果显示，该复合材料中氧占复合材料的重量百分比为 1%。 According to the results of conventional chemical analysis, nano-In in the nano-In / HCS10E composites accounts for the total The percentage by weight is 30%. According to the scanning electron microscope experiment results, the average particle size of In deposited on the outer surface of HCS10E is 10 nm, and the percentage of free In to the total weight of metal In is 5%. Based on the pore volume change and alloy density calculated by BET, the percentage of In on the outer surface to the total weight of metal In is 60%, and the percentage of In on the inner surface to the total weight of metal In is 35%. Sizes range from 1nm to 5nm. EDAX results show that the weight percentage of oxygen in the composite material is 1%.

实施例 11 Example 11

按照实施例 2所述的制备方法，制备纳米 Zn^Mg^/HCSlOE复合材料。所不同之处在于：歩骤 1中的金属氯化物溶液为 Ζηα₂溶液；所用还原剂为超细 Mg粉 (纯度 99.5%，粒度为 lum) 。步骤 2中所用原料碳粉为粒度为 10um的 HCS10E, 碳粉的加入量为 22g。 According to the preparation method described in Example 2, a nano-Zn ^ Mg ^ / HCSlOE composite material is prepared. The differences are as follows: The metal chloride solution in step 1 is a Zηα ₂ solution; the reducing agent used is an ultra-fine Mg powder (99.5% purity, particle size lum). The raw material carbon powder used in step 2 is HCS10E with a particle size of 10um, and the added amount of the carbon powder is 22g.

根据常规化学分析的结果，纳米 Zn^Mg^/HCSlOE复合材料中纳米 Z_¾95Mg。.。₅占该复合材料总重量的百分比为 30%。根据扫描电镜实验结果，沉积在外表面上的 Ζηο.₉₅Μ_&.。₅的平均颗粒尺寸为 220nm，游离的合金占合金总重量的比例为 5%。根据 BET测定的微孔体积变化及合金密度计算，外表面上的 Z_¾95Mg_M5占合金总重量的 85%，内表面上的 Zn。.₉₅Mg_M5占合金总重量的 10%，填充孔内的合金尺寸从 lnm到 25nm。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 0.2%。 According to the results of conventional chemical analysis, nano-Z ^ ₉₅ Mg in nano-Zn ^ Mg ^ / HCSlOE composites. .. ₅ is 30% of the total weight of the composite material. According to the results of SEM experiments, Znη. ₉₅ Μ _& . Deposited on the outer surface. The average particle size of ₅ is 220 nm, and the proportion of the free alloy to the total alloy weight is 5%. According to the pore volume change measured by BET and the alloy density calculation, Z _¾95 Mg _M5 on the outer surface accounts for 85% of the total weight of the alloy, and Zn on the inner surface. ₉₅ Mg _M5 accounts for 10% of the total weight of the alloy, and the size of the alloy in the filled hole ranges from 1nm to 25nm. EDAX results show that the weight percentage of oxygen in the composite material is 0.2%.

实施例 12 Example 12

按照实施例 1所述的制备方法，制备纳米 Sn^Fe^Zn^合金 /CMS28复合材料。所不同之处在于：步骤 1中的原料 SbCl₃替换为 FeCl₂，所配制的混合金属氯化物溶液中 SnCl₂的浓度为 0.6M， FeCl₂的浓度为 0.4M; 所用还原剂为超细 Zn粉 (纯度为 99.9%, 粒度为 20nm)，其用量为所需化学计量的 105%。歩骤 2中所用原料碳粉为粒度为 6um的 CMS28, 碳粉的加入量为 56g。根据常规化学分析的结果，纳米 S_{n 58}Fe_Q.₄Z_n。.。₂合金 /CMS28复合材料中纳米 Sn₀.₅₈Fe₀.₄Zn₀.₀₂合金占该复合材料总重量的百分比为 35%，合金的颗粒尺寸为 160nm, 游离的合金占合金总重量的百分比为 5%。该复合材料中氧占复合材料的重量百分比为 3%。 According to the preparation method described in Example 1, a nano Sn ^ Fe ^ Zn ^ alloy / CMS28 composite material was prepared. The differences are as follows: the raw material SbCl ₃ in step 1 is replaced with FeCl ₂ , the concentration of SnCl ₂ in the prepared mixed metal chloride solution is 0.6M, and the concentration of FeCl ₂ is 0.4M; the reducing agent used is ultrafine Zn Powder (purity is 99.9%, particle size is 20nm), and its amount is 105% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 6um, and the amount of carbon powder added is 56g. According to the results of conventional chemical analysis, the nano-Sn ₅₈ Fe _Q. ₄ Z _n . .. _The percentage of nano Sn _0. ₅₈ Fe _0. ₄ Zn _0. ₀₂ alloy in the ₂ alloy / CMS28 composite material is 35% of the total weight of the composite material, the particle size of the alloy is 160nm, and the percentage of the free alloy in the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 3%.

实施例 13 Example 13

按照实施例 1所述的制备方法，制备纳米 Sn。₇₈Ag_Q.₂Zno.。₂合金 /CMS28复合材料。所不同之处在于：歩骤 1中的原料 SbCl₃替换为 AgN0₃，所配制的混合金属盐溶液中 SnCl₂½浓度为 0.8M, 八_§ 0₃的浓度为 0.2M; 所用还原剂为超细 Zn粉 (纯度为 99.9%, 粒度为 20nm)，其用量为所需化学计量的 105%。歩骤 2中所用原料碳粉为粒度为 10um的 CMS28。 According to the preparation method described in Example 1, nano-Sn was prepared. ₇₈ Ag _Q. ₂ Zno .. ₂ alloy / CMS28 composite. The differences are as follows: The raw material SbCl ₃ in step 1 is replaced with AgN0 _{3. The} concentration of SnCl ₂ ½ in the prepared mixed metal salt solution is 0.8M, and the concentration of eight _§ 0 ₃ is 0.2M. The reducing agent used is super Fine Zn powder (99.9% purity, 20nm particle size), the amount of which is 105% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 10um.

根据常规化学分析的结果，纳米 Sno^Ag^Zno^合金 /CMS28复合材料中纳米 Sn₀.₇₈Ag₀.₂Zn₀₀₂合金占该复合材料总重量的百分比为 28%，合金的颗粒尺寸为 lOOnm, 游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 2%。 According to the results of conventional chemical analysis, the percentage of nano Sn _0. ₇₈ Ag _0. ₂ Zn ₀₀₂ alloy in the nano-Sno ^ Ag ^ Zno ^ alloy / CMS28 composite material to the total weight of the composite material is 28%, and the particle size of the alloy is 100 nm The proportion of free alloy to the total alloy weight is 5%. The weight percentage of oxygen in the composite material is 2%.

实施例 14 Example 14

按照实施例 1所述的制备方法，制备纳米8 ₄₈81¾.₅八1。.。₂合金^0复合材料。所不同之处在于：步骤 1中所用还原剂为超细 A1粉 (纯度为 99.9%，粒度为 lum)，其用量为所需化学计量的 90%。歩骤 2中所用原料碳粉为粒度为 15um的天然石墨 (NG) (产地中国南墅，其比表面积为 0.5m²/g，'不含微孔)。 ₅八 1。 According to the preparation method described in Example 1, nano 8 ₄₈ 81 ¾. ₅ eight 1 was prepared. .. ₂ alloy ^ 0 composite material. The difference is that: the reducing agent used in step 1 is ultra-fine A1 powder (purity is 99.9%, particle size is lum), and the amount is 90% of the required stoichiometry. The raw material carbon powder used in step 2 is a natural graphite (NG) with a particle size of 15um (origin is Nanshu, China, its specific surface area is 0.5m ² / g, 'without micropores).

根据常规化学分析的结果，纳米 Sno.₄₈Sb。.₅ Α1。 ₂合金/ NG复合材料中纳米 Sn_o.₄₈Sb_{O 5}Al₀₀₂合金占该复合材料总重量的百分比为 30%，合金的颗粒尺寸为 90nm, 游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 1%。采用实施例 1相同的方法，将复合材料制备成电极，并采用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1相同的测试方法进行测试，实验数据示于表 1中。 Based on the results of conventional chemical analysis, nano Sno. ₄₈ Sb. . ₅ Α1. The percentage of nano Sn _o . ₄₈ Sb _{O 5} Al ₀₀₂ alloy in the ₂ alloy / NG composite material is 30% of the total weight of the composite material, the particle size of the alloy is 90nm, and the proportion of the free alloy to the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 1%. Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.

实施例 15 Example 15

按照实施例 2所述的制备方法，制备纳米 Sn。.₅Sb ₅合金 /PCG复合材料。所不同之处在于：歩骤 1中所用还原剂为超细 Zn粉 (纯度为 99.9%，粒度为 lum)，其用量为所需化学计量的 95%。歩骤 2中所用原料碳粉为粒度为 25um的石油焦包覆的天然石墨（PCG) (日本大阪煤气公司，比表面积为 4mVg，不含微孔）；共还原反应温度为 200°C。 According to the preparation method described in Example 2, nano-Sn was prepared. ₅ Sb ₅ alloy / PCG composite. The differences are as follows: The reducing agent used in step 1 is ultra-fine Zn powder (purity is 99.9%, particle size is lum), and the amount is 95% of the required stoichiometry. The raw material carbon powder used in step 2 is petroleum coke-coated natural graphite (PCG) with a particle size of 25um (Osaka Gas Company, Japan, specific surface area is 4mVg, excluding micropores); the co-reduction reaction temperature is 200 ° C.

根据常规化学分析的结果，纳米 S_¾5Sb。.₅合金 /PCG复合材料中纳米 S_¾5Sb。.₅合金占该复合材料总重量的百分比为 32%，合金的颗粒尺寸为 240nm, 游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 2%。 According to the results of conventional chemical analysis, nano S _{¾ 5} Sb. . Nano S _¾5 Sb in ₅ alloy / PCG composites. The percentage of the ₅ alloy to the total weight of the composite material is 32%, the particle size of the alloy is 240nm, and the proportion of the free alloy to the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 2%.

釆用实施例 1相同的方法，将复合材料制备成电极，并采用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1相同的测试方法进行测试，实验数据示于表 1中。 (2) Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. An experimental battery was assembled as in Example 1. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.

实施例 16 Example 16

按照实施例 1所述的制备方法，制备纳米 Sn。.₅Sb。₅合金 /GPCF28复合材料。所不同之处在于：步骤 2中所用原料碳粉为 GPCF28(2800°C石墨化沥青基碳纤维，吉林碳素厂，直径为 10μιη，长为 60-300μιη，平均 ΙΟΟμηι, 比表面积为 10m²/g，不含微孔)。 According to the preparation method described in Example 1, nano-Sn was prepared. . ₅ Sb. ₅ alloy / GPCF28 composite material. The difference is that the raw material carbon powder used in step 2 is GPCF28 (2800 ° C graphitized pitch-based carbon fiber, Jilin Carbon Factory, with a diameter of 10 μm, a length of 60-300 μm, an average of 100 μm, and a specific surface area of 10 m ² / g , Without micropores).

根据常规化学分析的结果，纳米 Sno.₅Sb。.₅合金 /GPCF28复合材料中纳米 Sn。₅Sb。₅合金占该复合材料总重量的百分比为 30%，合金的颗粒尺寸为 60nm，游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 1%。 Based on the results of conventional chemical analysis, nano Sno. ₅ Sb. . Nano Sn in ₅ alloy / GPCF28 composites. ₅ Sb. The percentage of the alloy _{5 to the} total weight of the composite material is 30%, the particle size of the alloy is 60nm, and the proportion of the free alloy to the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 1%.

实施例 17 按照实施例 1所述的制备方法，制备纳米8_¾.₇₇8。.₂₂∑_¾。₁合金/0^828复合材料。所不同之处在于：歩骤 1中原料 SbCl₃替换为 BC1₃, 所配制的氯化物溶液中 SnCl₂的浓度为 0.8M, BC1^ 浓度为 0.2M; 所用还原剂为超细 Zn粉 (纯度为 99.9%，粒度为 lum) , 其用量为所需化学计量的 100%。歩骤 2中所用原料碳粉为粒度为 6um的 CMS28, 碳粉的加入量为 54g。 Example 17 According to the preparation method described in Example 1, nano 8 _¾ . ₇₇ 8 was prepared. . ₂₂ ∑ _¾ . ₁ alloy / 0 ^ 828 composite material. The differences are as follows: The raw material SbCl _{3 is} replaced by BC1 ₃ in Step 1. The concentration of SnCl ₂ in the prepared chloride solution is 0.8M, and the concentration of BC1 ^ is 0.2M. The reducing agent used is ultrafine Zn powder (purity It is 99.9%, the particle size is lum), and the amount is 100% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 6um, and the amount of carbon powder added is 54g.

根据常规化学分析的结果，纳米 8 .₇₇8。.₂^11。.。,合金/0^828复合材料中纳米 Sn₀.₇₇B₀.₂₂Zn₀₀₁合金占该复合材料总重量的百分比为 35%，合金的颗粒尺寸为 120nm，游离的合金占合金总重量的比例为 2%。该复合材料中氧占复合材料的重量百分比为 2%。 According to the results of conventional chemical analysis, the nanometer 8. ₇₇ 8. . ₂ ^ 11. .. , The nano Sn _0. ₇₇ B _0. ₂₂ Zn ₀₀₁ alloy in the alloy / 0 ^ 828 composite material accounts for 35% of the total weight of the composite material, the particle size of the alloy is 120nm, and the ratio of the free alloy to the total weight of the alloy is 2%. The weight percentage of oxygen in the composite material is 2%.

实施例 18 Example 18

按照实施例 1所述的制备方法，制备纳米S_¾84B。.,Si。.。₅Zn₀._m合金/CMS28复合材料。所不同之处在于：歩骤 1中的原料 SbCl₃替换为 BCl^BSiCl₄，所配制的氯化物溶液中 SnCl₂的浓度为 0.85M, BC1₃的浓度为 0.1M, 8^：1₄的浓度为 0.01M; 所用还原剂为超细 Zn粉 (纯度为 99.9%，粒度为 lum)，其用量为所需化学计量的 100%。歩骤 2 中所用原料碳粉为粒度为 6um的 CMS28, 碳粉的加入量为 64g。 According to the preparation method described in Example 1, nano S _{¾ 84} B was prepared. ., Si. .. ₅ Zn _0. _M alloy / CMS28 composite. The difference is that the raw material SbCl ₃ in step 1 is replaced with BCl ^ BSiCl ₄ , the concentration of SnCl ₂ in the prepared chloride solution is 0.85M, the concentration of BC1 ₃ is 0.1M, and 8 ^: 1 ₄ The concentration is 0.01M; the reducing agent used is ultrafine Zn powder (purity is 99.9%, particle size is lum), and the amount is 100% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 6um, and the amount of carbon powder added is 64g.

根据常规化学分析的结果，纳米8_¾848。.^。.。₅211₀.。₁合金/0^28复合材料中纳米 8 ₈₄8。.^₍₎.₍₎₅21_½.。₁合金占该复合材料总重量的百分比为32%，合金的颗粒尺寸为 120nm, 游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 10%。 According to the results of conventional chemical analysis, nano 8 _{¾ 84} 8. . ^. .. ₅ 211 ₀ ... ₁ alloy / 0 ^ 28 composite in the nano 8 ₈₄ 8. . ^ ₍₎ . _{() 5} 21 _½ .. The percentage of ₁ alloy to the total weight of the composite material is 32%, the particle size of the alloy is 120nm, and the proportion of the free alloy to the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 10%.

实施例 19 Example 19

按照实施例 1所述的制备方法，制备纳米8_¾80)。.^。._|合金 ]\ 828复合材料。所不同之处在于：歩骤 1中的原料 SbCl₃替换为 CoCl^BNiCl₂，所配制的氯化物溶液中 SnCl₂的浓度为 0.8M， CoCl₂的浓度为 0.1M， NiCl₂ 浓度为 0.1M; 所用还原剂为超细 Zn粉 (纯度为 99.9%，粒度为 20nm)，其用量为所需化学计量的 100%。歩骤 2中所用原料碳粉为粒度为 6um的 CMS28。 Prepared according to the method of Example 1, preparation of nano ₈ ¾8 0). . ^. . _| Alloy] \ 828 composite materials. The difference is that: raw material in step SbCl ₃ was replaced ho CoCl ^ BNiCl _2, formulated chloride solution of SnCl ₂ in a concentration of 0.8M, CoCl ₂ concentration of 0.1M, NiCl ₂ at a concentration of 0.1M ; The reducing agent used is Ultrafine Zn powder (purity is 99.9%, particle size is 20nm), and its amount is 100% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 6um.

根据常规化学分析的结果，纳米 Sn^Co^Nia 合金 /CMS28复合材料中纳米 8 ₈0>₍₎.₁>«₍₎._|合金占该复合材料总重量的百分比为 25%, 合金的颗粒尺寸为 80nm，游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 2%。 According to the results of conventional chemical analysis, nano 8 ₈ 0> ₍₎ . ₁ > « ₍₎ . In the nano Sn ^ Co ^ Nia alloy / CMS28 composite material _| The percentage of the alloy to the total weight of the composite material is 25%, the particles of the alloy The size is 80 nm, and the ratio of the free alloy to the total alloy weight is 5%. The weight percentage of oxygen in the composite material is 2%.

实施例 20 Example 20

按照实施例 1所述的制备方法，制备纳米 Sn^Sb^Ti^合金 /CMS28复合材料。所不同之处在于：歩骤 1中的氯化物增加了 TiCl₄，所配制的氯化物溶液中 8110₂的浓度为 0.45M, 31^1₃的浓度为 0.5M, 1 0₄的浓度为 0.05M; 所用还原剂为超细 Zn 粉 (纯度为 99.9%, 粒度为 20nm)，其用量为所需化学计量的 100%。步骤 2中所用原料碳粉为粒度为 6um的 CMS28。 According to the preparation method described in Example 1, nano-Sn ^ Sb ^ Ti ^ alloy / CMS28 composite material was prepared. The difference is that: in step 1 ho increased chloride TiCl _4, the concentration of the chloride solution prepared as _81,102 0.45M, concentration of 31 ^ ₁₃ is the concentration of 0.5M, 1 0 ₄ 0.05 M; The reducing agent used is ultra-fine Zn powder (purity is 99.9%, particle size is 20nm), and the amount is 100% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 6um.

根据常规化学分析的结果，纳米8 ₄₅81¾.₅1 。₅合金 ^^28复合材料中纳米 Sn。₄₅Sb。₅Ti。.。₅合金占该复合材料总重量的百分比为 29%，合金的颗粒尺寸为 80nm，游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 2%。 According to the results of conventional chemical analysis, the nanometer 8 ₄₅ 81¾. ₅ 1. Nano-Sn in ₅ alloy ^^ 28 composites. ₄₅ Sb. ₅ Ti. .. The percentage of the ₅ alloy to the total weight of the composite material is 29%, the particle size of the alloy is 80 nm, and the proportion of the free alloy to the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 2%.

实施例 21 . Embodiment 21.

按照实施例 1所述的制备方法，制备纳米 Sn。₇₈V。.₂Zn_M2合金 /CMS28复合材料。所不同之处在于：步骤 1中的原料 SbCl₃替换为 VC1₄，所配制的氯化物溶液中 SnCl₂ 的浓度为 0.8M， 0₄的浓度为 0.2M; 所用还原剂为超细 Zn粉 (纯度为 99.9%，粒度为 20nm), 其用量为所需化学计量的 100%。歩骤 2中所用原料碳粉为粒度为 6um的根据常规化学分析的结果，纳米 Sn^V^Zn^合金 /CMS28复合材料中纳米 Sn₀.₇₈V₀,Zn₀.₀₂合金占该复合材料总重量的百分比为 25%，合金的颗粒尺寸为 lOOnm, 游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 6%。 According to the preparation method described in Example 1, nano-Sn was prepared. ₇₈ V. . ₂ Zn _M2 alloy / CMS28 composite. The difference is that the raw material SbCl ₃ in step 1 is replaced with VC1 _4. The concentration of SnCl ₂ in the prepared chloride solution is 0.8M and the concentration of 0 ₄ is 0.2M. The reducing agent used is ultrafine Zn powder ( The purity is 99.9% and the particle size is 20nm), and the amount is 100% of the required stoichiometry. The raw material carbon powder used in step 2 is a particle size of 6um. According to the results of conventional chemical analysis, the nano-Sn ^ V ^ Zn ^ / CMS28 The percentage of Sn _0. ₇₈ V ₀ , Zn _0. ₀₂ alloy to the total weight of the composite material is 25%, the particle size of the alloy is 100 nm, and the proportion of free alloy to the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 6%.

实施例 22 Example 22

按照实施例 1所述的制备方法，制备纳米 Sno^Mn^Zno^合金 /CMS28复合材料。所不同之处在于：步骤 1中的原料 SbCl₃替换为 MnCl₂，所配制的氯化物溶液中 SnCl S浓度为 0.8M , 1\¾^1₂的浓度为 0.2M ; 所用还原剂为超细 Zn粉（纯度为 99.9%，粒度为 20nm)，其用量为所需化学计量的 100%。歩骤 2中所用原料碳粉为粒度为 6um的 CMS28。 According to the preparation method described in Example 1, a nano Sno ^ Mn ^ Zno ^ alloy / CMS28 composite material was prepared. The difference is that: the raw material SbCl ₃ in step 1 is replaced with MnCl ₂ , the concentration of SnCl S in the prepared chloride solution is 0.8M, and the concentration of 1 \ ¾ ^ 1 ₂ is 0.2M; the reducing agent used is ultrafine Zn powder (purity is 99.9%, particle size is 20nm), and its amount is 100% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 6um.

根据常规化学分析的结果，纳米 S_n。.₇₈M_n().₂Zn₀.。₂合金/CMS28复合材料中纳米 Sn₀.₇₈Mn₀.₂Zn₀.₀₂合金占该复合材料总重量的百分比为 25%，合金的颗粒尺寸为 150nm，游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 8%。 The results of chemical analysis of a conventional nano S _n. ₇₈ M _{n ()} . ₂ Zn ₀ . _The percentage of nano Sn _0. ₇₈ Mn _0. ₂ Zn _0. ₀₂ alloy in the ₂ alloy / CMS28 composite material is 25% of the total weight of the composite material, the particle size of the alloy is 150 nm, and the ratio of the free alloy to the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 8%.

实施例 23 Example 23

按照实施例 1所述的制备方法，制备纳米811。.₅₍^。.₄₉2¾.。₁合金/1^810复合材料。所不同之处在于：歩骤 1中的原料 SbCl₃替换为 SiCl_{4 ;} 所用还原剂为超细 Zn粉 (纯度为 99.9%，粒度为 lum)，其用量为所需化学计量的 100%。歩骤 2中所用原料碳粉为粒度为 lOum的 HCS10,碳粉的加入量为 46g。 According to the preparation method described in Example 1, nano-811 was prepared. _{5 (} ^ .. ₄₉ 2¾ .. ₁ alloy / 1 ^ 810 composite. The difference is that the raw material SbCl ₃ in step 1 is replaced by SiCl _4; the reducing agent used is ultra-fine Zn powder (purity 99.9%). %, Particle size is lum), and its amount is 100% of the required stoichiometry. The raw material carbon powder used in step 2 is HCS10 with a particle size of 10um, and the added amount of carbon powder is 46g.

根据常规化学分析的结果，纳米 S_{n 5}。Si ₄₉Zn _Q1合金 /HCS10复合材料中纳米 Sn₀.₅₀Si₀.₄₉Zn₀.₀₁合金占该复合材料总重量的百分比为 25%，合金的颗粒尺寸为 lOOnm, 游离的合金占合金总重量的比例为 5%。该复合材料中氧占复合材料的重量百分比为 8%。 According to the results of conventional chemical analysis, nano Sn ₅ . Nano-Sn _0. ₅₀ Si _0. ₄₉ Zn _0. ₀₁ alloy in Si ₄₉ Zn _Q1 alloy / HCS10 composites accounts for 25% of the total weight of the composite, the particle size of the alloy is 100 nm, and the free alloy accounts for the total weight of the alloy The percentage is 5%. The weight percentage of oxygen in the composite material is 8%.

采用实施伊 j l相同的方法，将复合材料制备成电极，并采用如实施例 1所述的两电极实验扣式电池 2016型研究该复合材料作为二次锂电池负极活性材料的电化学性能，如实施例 1组装成实验电池。采用如实施例 1相同的测试方法进行测试，实验数据示于表 1中。 The composite material was prepared into an electrode using the same method as that described in Example 1, and the method described in Example 1 was used. The two-electrode experimental button cell type 2016 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.

实施例 24 Example 24

纳米 Sn。.₅Sb_Q.₅合金 /HCS10复合材料也可通过水热还原法制备，步骤如下- ( 1 ) 将 SbCl₃和SnCl₂.H₂0按 1 :1摩尔比混合后，溶于乙醇中形成 0.1M180ml的混合金属氯化物溶液，然后将 12g平均粒度为 lOum的球形热解硬碳 HCS10加入到上述溶液中，并搅拌均匀，得到一个混合液。（2 ) 将上述（1 ) 的混合液加入到一容积为 200ml的压力釜中，以 100°C/小时的速度加热到 200°C，然后恒温 12小时，再自然冷却到室温后，取出产物。（3 ) 将歩骤（2 ) 的产物过滤，并用乙醇清洗，直到用硝酸银检测不到滤液中的 cr离子。滤渣真空干燥后，将其置入管式炉中，以 50°C/小时的速度加热到 250°C，恒温 10小时，然后自然冷却到室温。在加热、恒温、降温过程中始终通入 H₂/Ar混合气，其中 H₂占总体积的 8%，流速为 2ml/min。最终得到纳米 Sn。.₅Sb。.₅合金 /HCS10复合材料样品。 Nano Sn. ₅ Sb _Q. ₅ alloy / HCS10 composite can also be prepared by hydrothermal reduction method, the steps are as follows-(1) SbCl ₃ and SnCl ₂ .H ₂ 0 are mixed at a molar ratio of 1: 1, and then dissolved in ethanol to form 0.1M 180 ml of a mixed metal chloride solution, and then 12 g of spherical pyrolytic hard carbon HCS10 with an average particle size of 10 um was added to the above solution and stirred to obtain a mixed solution. (2) Add the mixed solution of (1) above to a 200ml autoclave, heat it to 200 ° C at 100 ° C / hour, then keep it constant temperature for 12 hours, and then naturally cool to room temperature, then take out the product . (3) The product of step (2) is filtered and washed with ethanol until no cr ions in the filtrate can be detected with silver nitrate. After the filter residue is dried under vacuum, it is placed in a tube furnace, heated to 250 ° C at a rate of 50 ° C / hour, kept constant for 10 hours, and then naturally cooled to room temperature. During the process of heating, constant temperature, and cooling, H ₂ / Ar mixed gas is always introduced, in which H ₂ accounts for 8% of the total volume, and the flow rate is 2 ml / min. Finally, nano Sn was obtained. . ₅ Sb. . ₅ alloy / HCS10 composite samples.

根据常规化学分析的结果，该纳米 Sno.₅Sb。.₅合金 /HCS 10复合材料中纳米 Sn_{fl 5}Sb ₅合金占 HCS10的重量百分比为 35%。扫描电镜显示合金颗粒大小为 30nm，不含游离的 Sn。₅Sb。.₅合金。 EDAX结果显示，该复合材料中氧占复合材料的重量百分比为 10%。 BET测量该复合材料的微孔比表面积减少为 50m²/g，说明一部分纳米合金占据了内部孔。 According to the results of conventional chemical analysis, the nano Sno. ₅ Sb. . The weight percentage of nano Sn _{fl 5} Sb ₅ alloy in the ₅ alloy / HCS 10 composite material is 35% by weight. Scanning electron microscopy showed that the alloy particles were 30 nm in size and contained no free Sn. ₅ Sb. . ₅ alloy. EDAX results show that the weight percentage of oxygen in the composite material is 10%. The pore specific surface area of the composite material was reduced by BET to 50 m ² / g, indicating that a portion of the nano-alloys occupied the internal pores.

Claims

权利要求 Rights request

1 . 一种纳米金属或纳米合金 /碳复合材料，其特征在于：纳米金属或纳米合金颗粒沉积在碳颗粒的外表面和具有孔结构的内表面，其中纳米金属或纳米合金颗粒的平均尺寸为 l~250nm，碳颗粒的平均尺寸为 lum~50um，纳米金属或纳米合金颗粒与碳颗粒的重量百分比为 10%~70%； 1. A nano metal or nano alloy / carbon composite material, characterized in that: nano metal or nano alloy particles are deposited on an outer surface of a carbon particle and an inner surface having a pore structure, wherein an average size of the nano metal or nano alloy particle is l ~ 250nm, the average size of carbon particles is lum ~ 50um, the weight percentage of nano metal or nano alloy particles and carbon particles is 10% ~ 70%;

所述的纳米金属为 Sn、 Sb、 In或 Zn之中的任意一种； The nano metal is any one of Sn, Sb, In or Zn;

所述的纳米合金的表达式定义为 M'_xlM² _x2...Mⁿ _xn，其中 M'、 M²...Mⁿ表示不同的元素，并至少含有 Sn、 Sb、 In或 Zn之中的任意一种，也可以含有主族元素中的 Mg、 B、 Al、 Si及过渡金属族的 Ti、 V、 Mn、 Fe、 Co、 Ni、 Cu或 Ag; 其中下标 xl、 x2...xn代表不同元素原子占纳米合金所有元素原子总摩尔数的摩尔百分比， xl+x2+...+xn=l , xl、 x2、 ...xn的取值为 0~1之间，且 Sn、 Sb、 In或 Zn四种元素摩尔百分比的和不低于 50%; 其中 n为 1~16的整数； The expression of the nano-alloy is defined as M ' _xl M ² _x2 ... M ⁿ _xn , where M', M ² ... M ⁿ represent different elements and contain at least Sn, Sb, In or Zn. Any of these may also contain Mg, B, Al, Si in the main group element, and Ti, V, Mn, Fe, Co, Ni, Cu, or Ag in the transition metal group; where the subscripts xl, x2 .. .xn represents the mole percentage of atoms of different elements to the total number of moles of all elements of the nano-alloy, xl + x2 + ... + xn = l, xl, x2, ... xn are between 0 and 1, and Sn The sum of the molar percentages of the four elements Sb, In, or Zn is not less than 50%; where n is an integer from 1 to 16;

2. 按权利要求 1所述的纳米金属或纳米合金 /碳复合材料，其特征在于：所述的碳材料是天然石墨、石墨化中间相碳小球、针状焦，微孔硬炭球或碳纤维。 2. The nano-metal or nano-alloy / carbon composite material according to claim 1, characterized in that the carbon material is natural graphite, graphitized mesophase carbon spheres, needle coke, microporous hard carbon spheres or carbon fiber.

3. 按权利要求 1或 2所述的纳米金属或纳米合金 /碳复合材料，其特征在于- 所述的碳材料通过 Brunauer-E匪 ett- Teller方法测定的比表面积在 0.1~3000 m²/g，其中外表面积为 0. l~50m²/g，内表面积为 0. l~3000m²/g。 3. The nano-metal or nano-alloy / carbon composite material according to claim 1 or 2, characterized in that-the specific surface area of the carbon material measured by the Brunauer-E-Bettett-Teller method is 0.1 to 3000 m ² / g, wherein the outer surface area is 0.1 to 50 m ² / g, and the inner surface area is 0.1 to 3000 m ² / g.

4. 按权利要求 1所述的纳米金属或纳米合金 /碳复合材料，其特征在于：所述的纳米金属或纳米合金 /碳复合材料中，不与碳颗粒的外表面接触，处于游离状态的纳米金属或纳米合金占纳米金属或纳米合金总重量的百分比为 0.1~30%。 4. The nano-metal or nano-alloy / carbon composite material according to claim 1, wherein the nano-metal or nano-alloy / carbon composite material is in a free state without contacting the outer surface of the carbon particles. The percentage of nano metal or nano alloy to the total weight of nano metal or nano alloy is 0.1-30%.

5. 按权利要求 1所述的纳米金属或纳米合金 /碳复合材料，其特征在于：其中所述的纳米金属或纳米合金为 Sn。.₅。Sb。 ₅。合金、 Sno.₈₈Sb_{Q 12}合金、 Sno.₄₄Sb。 ₁₆Cu。₄合余、 Sn。₄Zn。₅₅0_Q。₅合金、 Sb、 In、 Sn或 Zn。 5. The nano-metal or nano-alloy / carbon composite material according to claim 1, wherein: the nano-metal or nano-alloy is Sn. . ₅ . Sb. ₅ . Alloy, Sno. ₈₈ Sb _{Q 12} alloy, Sno. ₄₄ Sb. ₁₆ Cu. ₄ surplus, Sn. ₄ Zn. ₅₅ 0 _Q. ₅ alloy, Sb, In, Sn or Zn.

6. 按权利要求 1所述的纳米金属或合金 /碳复合材料，其特征在于：所述的复合材料中允许少量氧的存在，氧占复合材料总重量的百分比为 0.001%~10%。 6. The nanometal or alloy / carbon composite material according to claim 1, wherein a small amount of oxygen is allowed in the composite material, and the percentage of oxygen in the total weight of the composite material is 0.001% to 10%.

7. 一种权利要求 1~6所述的纳米金属或纳米合金 /碳复合材料的制备方法，包括以下步骤： 7. A method for preparing a nano metal or nano alloy / carbon composite material according to claims 1 to 6, comprising the following steps:

1. 反应液配制： 1. Reaction solution preparation:

①配制氯化物溶液：将一种或几种氯化物混合后，溶于一种 C1-C4的醇中，形成浓度为 0.01~3M的氯化物溶液； ① Preparation of chloride solution: After mixing one or more chlorides, dissolve in a C1-C4 alcohol to form a concentrated solution. Chloride solution with a degree of 0.01 ~ 3M;

其中氯化物为 Sn、 Sb、 In、 Zn或主族元素中的 Mg、 B、 Al、 Si或过渡金属族元素中的 Ti、 V、 Mn、 Fe、 Co、 Ni、 Cu、 Ag的氯化物，并至少含有 Sn、 Sb、 In或 Zn 氯化物中的一种，且 Sn、 Sb、 In或 Zn的氯化物占所有氯化物的摩尔百分比的和不低于 50%; Wherein the chloride is a chloride of Sn, Sb, In, Zn or Mg, B, Al, Si in the main group element or Ti, V, Mn, Fe, Co, Ni, Cu, Ag in the transition metal group element, And contains at least one of Sn, Sb, In or Zn chloride, and the sum of the molar percentages of Sn, Sb, In or Zn to all chlorides is not less than 50%;

②配制还原悬浊液：将上述氯化物溶液中的阳离子全部还原为单质所需化学计量的 90%~105%量的 Zn粉、 Fe粉、 Mg粉或 A1粉中一种，加入到上述①相同的 C1-C4的醇中，所用醇的体积与氯化物溶液的体积比为 0.001-200，形成悬浊液； ② Preparation of reduction suspension: All the cations in the above chloride solution are reduced to one of Zn powder, Fe powder, Mg powder or A1 powder in the amount of 90% to 105% of the stoichiometry required for the element, and added to the above① In the same C1-C4 alcohol, the volume ratio of the volume of the alcohol to the chloride solution is 0.001-200 to form a suspension;

其中 Zn粉、 Fe粉、 Mg粉或 A1粉颗粒尺寸为 20nm-50um; The particle size of Zn powder, Fe powder, Mg powder or A1 powder is 20nm-50um;

2. 有机溶剂体系中共还原： 2. Co-reduction in organic solvent systems:

包括将碳粉加入上述歩骤（1 ) 配制的氯化物溶液中，在 -20°C~200°C的温度下，在 lmin-24h之内，用分液漏斗将上述歩骤（1 )配制的还原悬浊液全部滴加到氯化物溶液中，并同时搅拌； The method includes adding carbon powder to the chloride solution prepared in the above step (1), and preparing the above step (1) in a separation funnel at a temperature of -20 ° C to 200 ° C within 1min-24h. All of the reducing suspension was added dropwise to the chloride solution, while stirring;

或者将碳粉加入上述步骤（1 ) 配制的还原悬浊液中，在 -20°C~200°C的温度下，在 lmin-24h时间内，用分液漏斗将上述步骤（1 ) 配制的氯化物溶液全部滴加到还原悬浊液中，并同时搅拌； Or add carbon powder to the reducing suspension prepared in the above step (1), and use a separatory funnel to mix the prepared in the above step (1) at a temperature of -20 ° C ~ 200 ° C for 1min-24h. The entire chloride solution was added dropwise to the reducing suspension, while stirring;

其中上述歩骤 1配制的氯化物溶液中所含阳离子的重量与碳粉的重量比为 10%~70%； Wherein, the weight ratio of the cation to the carbon powder in the chloride solution prepared in the above step 1 is 10% to 70%;

3. 分离、洗涤并干燥： 3. Isolate, wash and dry:

将上述歩骤 2共还原反应后的混合物过滤；再用乙醇洗涤，直到用硝酸银检测不到滤液中的 C1离子；然后将得到的粉末在真空 O.OhmnHg-lOmmHg下， 50~120°C，干燥 1〜48小时后，得到纳米金属或纳米合金 /碳复合材料，并将该材料保存在惰性环境或真空中。 The mixture after the co-reduction reaction in step 2 was filtered; washed with ethanol until the C1 ion in the filtrate was not detected with silver nitrate; and the obtained powder was vacuumed at O. OhmnHg-10mmHg, 50 ~ 120 ° C After drying for 1 to 48 hours, a nano-metal or nano-alloy / carbon composite material is obtained, and the material is stored in an inert environment or in a vacuum.

8. 按权利要求 7所述的纳米金属或纳米合金 /碳复合材料的制备方法，其特征在于：所述的 C1-C4的醇为甲醇、乙醇、乙二醇、异丙醇、丙三醇或丁醇。 8. The method for preparing a nano-metal or nano-alloy / carbon composite material according to claim 7, characterized in that: the C1-C4 alcohol is methanol, ethanol, ethylene glycol, isopropanol, glycerin Or butanol.

9. 按权利要求 7所述的纳米金属或纳米合金 /碳复合材料的制备方法，其特征在于：所述的在有机溶剂体系中共还原反应在 -10。C~50°C的温度下进行。 9. The method for preparing a nano-metal or nano-alloy / carbon composite material according to claim 7, characterized in that: the co-reduction reaction in an organic solvent system is at -10. C ~ 50 ° C.

10. 一种纳米金属或纳米合金 /碳复合材料在二次锂电池中的应用，其特征在于：作为二次锂电池的负极活性材料。 10. The application of a nano-metal or nano-alloy / carbon composite material in a secondary lithium battery, which is characterized in that it is used as a negative active material for a secondary lithium battery.