WO2019019409A1

WO2019019409A1 - Lithium alloy-skeletal carbon composite material and preparation method therefor, negative electrode and secondary battery

Info

Publication number: WO2019019409A1
Application number: PCT/CN2017/105656
Authority: WO
Inventors: 康拓; 陈立桅; 卢威; 沈炎宾; 王亚龙; 郭峰; 刘承浩; 陈鹏
Original assignee: 中能中科（天津）新能源科技有限公司
Priority date: 2017-07-26
Filing date: 2017-10-11
Publication date: 2019-01-31
Also published as: CN109309243A

Abstract

Disclosed are a lithium alloy-skeletal carbon composite material and a preparation method therefor, a negative electrode and a secondary battery. The lithium alloy-skeletal carbon composite material comprises a porous carbon material carrier and a lithium alloy formed on the surface of and in pores of the porous carbon material carrier. By compounding the lithium alloy and the skeletal carbon carrier, the wettability of lithium metal for skeletal carbon can be effectively improved, thereby improving the affinity of the lithium metal to the skeletal carbon and increasing the amount of lithium loading in the lithium material.

Description

锂合金-骨架碳复合材料及其制备方法、负极和二次电池Lithium alloy-skeletal carbon composite material and preparation method thereof, anode and secondary battery

技术领域Technical field

本发明涉及能源电池领域，具体而言，本发明提供一种锂合金-骨架碳复合材料及其制备方法、包含所述锂合金-骨架碳复合材料的负极和锂电池。The present invention relates to the field of energy batteries, and in particular, to a lithium alloy-skeletal carbon composite material, a method for preparing the same, a negative electrode including the lithium alloy-skeletal carbon composite material, and a lithium battery.

背景技术Background technique

锂离子电池，作为清洁能源的代表，已经广泛地应用于当今社会的各个领域。锂离子电池由于具有高能量密度、环境友好性以及良好的循环稳定性等特性，因此受到人们的青睐。然而，随着社会的发展，传统的锂离子电池的能量密度已经无法满足人们日益增长的能耗要求。此外，环境污染问题是当今社会的最大的热门问题，目前社会的共识是开发出清洁的能源来代替传统的石油能源，因此开发出具有更高能量密度的锂动力电池是目前能源领域的重中之重。Lithium-ion batteries, as representatives of clean energy, have been widely used in various fields of today's society. Lithium-ion batteries are favored by people because of their high energy density, environmental friendliness and good cycle stability. However, with the development of society, the energy density of traditional lithium-ion batteries has been unable to meet the increasing energy requirements of people. In addition, the problem of environmental pollution is the biggest hot issue in today's society. At present, the consensus of the society is to develop clean energy to replace traditional petroleum energy. Therefore, the development of lithium-powered batteries with higher energy density is the focus of the current energy field. The weight.

由于金属锂负极具有十倍于传统石墨负极的比容量，达到了3860mAh/g，并且金属锂具有最负的电位和最轻的密度，因此采用锂负极的电池的能量密度将会有极大的提高。此外，锂金属负极可以为正极提供锂离子，因此可以和能量密度更高的无锂正极如硫、空气等组成高能量密度的锂硫-锂空气电池。若是该电池得以商业化，其能量密度就能够和汽油相媲美，因此环境问题将得到极大的改善。不幸的是，金属锂负极在循环过程中容易产生枝晶，随着电池工作的进行，不断生长的枝晶会刺穿电池隔膜而引起电池短路并放出巨大的热，引发燃烧、***等一系列安全事故。此外金属锂在充放电过程中表面的SEI层不断生长消耗活性物质和电解液，降低电池的循环寿命。Since the metal lithium negative electrode has ten times the specific capacity of the conventional graphite negative electrode, reaching 3860 mAh/g, and the metallic lithium has the most negative potential and the lightest density, the energy density of the battery using the lithium negative electrode will be extremely large. improve. In addition, the lithium metal negative electrode can provide lithium ions for the positive electrode, and thus can be combined with a lithium-ion positive electrode having a higher energy density such as sulfur, air, etc. to form a high-energy density lithium sulfur-lithium air battery. If the battery is commercialized, its energy density will be comparable to that of gasoline, so environmental problems will be greatly improved. Unfortunately, the metal lithium anode is prone to dendrites during the cycle. As the battery works, the growing dendrites will pierce the battery separator and cause the battery to short-circuit and release huge heat, causing combustion, explosion, etc. Security incident. In addition, during the charging and discharging process, the SEI layer of the metal lithium continuously grows and consumes the active material and the electrolyte, thereby reducing the cycle life of the battery.

美国FMC公司使用熔融乳化的再修饰的方法制备出可应用于锂电池负极材料的金属锂颗粒(参见US 8,021,496 B2、US 2013/0181160 A1、CN 102255080 A)。然而利用该方法制备出来的金属锂颗粒粒径为20-100微米，粒径较大并且分布较宽，不能够有效地抑制锂枝晶的产生。同时，该材料没有内部结构的支撑，在大容量的充放电过程中会产生巨大的体积变化，不利于电池的循环性能。中国科学院苏州纳米技术与纳米仿生研究所公开了一种金属锂-骨架碳复合材料及其制备方法、负极和二次电池(参见，PCT国际申请公开号WO 2015139660A1；中国专利申请号CN 201410395114.0)。其中，采用多孔骨架碳材料作为载体与熔融的金属锂混合，制备出粒径范围为1-100微米的金属锂-骨架碳复合材料，其安全性明显优于金属锂片。然而，金属锂与碳骨架的浸润性不佳，制备出的金属锂-骨架碳复合材料的载锂量低并且比容量低。此外Yi Cui课题组通过CVD方法在静电纺丝碳纤维薄膜表面通过沉积Si或ZnO来提高碳材料的亲锂性(参见，PNAS.1518188113，Nat.Commun.7:10992)。然而该方法需要CVD的复杂加工，短时间内难以大批量生产。U.S. FMC Corporation uses a remelting method of melt emulsification to prepare metal lithium particles which can be applied to a negative electrode material of a lithium battery (see US Pat. No. 8,021,496 B2, US 2013/0181160 A1, CN 102255080 A). However, the metal lithium particles prepared by the method have a particle diameter of 20-100 μm, a large particle size and a wide distribution, and cannot effectively inhibit the generation of lithium dendrites. At the same time, the material has no internal structure support, and a large volume change occurs during the large-capacity charging and discharging process, which is not conducive to the cycle performance of the battery. Suzhou Institute of Nanotechnology and Nano-Bionics, Chinese Academy of Sciences, discloses a metal lithium-skeletal carbon composite material, a preparation method thereof, a negative electrode and a secondary battery (see, PCT International) Application Publication No. WO 2015139660A1; Chinese Patent Application No. CN 201410395114.0). Among them, the porous lithium skeleton material is used as a carrier and mixed with molten lithium metal to prepare a metal lithium-skeletal carbon composite material with a particle size ranging from 1 to 100 micrometers, and the safety is obviously superior to that of the lithium metal sheet. However, the metal lithium and the carbon skeleton have poor wettability, and the prepared metal lithium-skeletal carbon composite material has a low lithium loading amount and a low specific capacity. In addition, the Yi Cui team improved the pro-lithium of the carbon material by depositing Si or ZnO on the surface of the electrospun carbon fiber film by a CVD method (see, PNAS. 1518188113, Nat. Commun. 7: 10992). However, this method requires complicated processing of CVD and is difficult to mass-produce in a short time.

因此，开发出一种能够提高骨架碳复合材料的载锂量、从而提高比容量的方法具有重要的意义。Therefore, it has been important to develop a method capable of increasing the amount of lithium supported by the skeleton carbon composite material and thereby increasing the specific capacity.

发明内容Summary of the invention

从以上阐述的技术问题出发，本发明的目的是通过采用熔融的锂合金与骨架碳混合，通过简单快捷的方法制备出锂合金-骨架碳复合负极，该材料提高金属锂与骨架碳的亲和力，提高材料的载锂量，并且进而提高了材料的比容量。Starting from the technical problems set forth above, the object of the present invention is to prepare a lithium alloy-skeletal carbon composite negative electrode by a simple and quick method by mixing a molten lithium alloy with a skeleton carbon, which improves the affinity of metallic lithium with the skeleton carbon. Increasing the amount of lithium supported by the material and, in turn, increasing the specific capacity of the material.

本发明人经过深入细致的研究，完成了本发明。根据本发明的技术方案，通过将一些特定的金属元素与熔融锂混合制备出锂合金的方法来降低金属锂的表面能，使得金属锂更容易在骨架碳上附着，从而得到了容量较高的锂合金-骨架碳复合材料。The inventors have completed the present invention through intensive research. According to the technical solution of the present invention, a method for preparing a lithium alloy by mixing some specific metal elements with molten lithium is used to reduce the surface energy of the metal lithium, so that the metal lithium is more easily attached to the skeleton carbon, thereby obtaining a higher capacity. Lithium alloy-skeletal carbon composite.

根据本发明的一个方面，提供了一种锂合金-骨架碳复合材料，所述锂合金-骨架碳复合材料包括多孔碳材料载体以及形成在所述多孔碳材料载体的表面上和孔隙内的锂合金。According to an aspect of the invention, there is provided a lithium alloy-skeletal carbon composite material comprising a porous carbon material support and lithium formed on a surface of the porous carbon material support and in the pores alloy.

根据本发明的另一个方面，提供了一种用于制备锂合金-骨架碳复合材料的方法，所述方法包括在惰性气氛下依次进行下列步骤：According to another aspect of the present invention, there is provided a method for producing a lithium alloy-skeletal carbon composite, the method comprising the following steps being carried out sequentially under an inert atmosphere:

(1)将金属锂加热到180-220℃的温度，以得到熔融锂；(1) heating lithium metal to a temperature of 180-220 ° C to obtain molten lithium;

(2)在500-800转/秒的转速的搅拌下，将步骤(1)中得到的熔融锂升温至220-1000℃，加入一种或多种元素熔炼得到熔融状态的锂合金，加入的所述元素选自镁、硅、硼、碳、氮、氧、氟、铝、磷、硫、氯、钙、锌、镓、锗、砷、硒、溴、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、铱、铂、金、汞、铊、铅、铋和钋中的一种或多种； (2) heating the molten lithium obtained in the step (1) to 220-1000 ° C under stirring at a rotation speed of 500-800 rpm, adding one or more elements to obtain a molten lithium alloy, and adding The element is selected from the group consisting of magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, gallium, antimony, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium. , one or more of indium, tin, antimony, bismuth, iodine, antimony, platinum, gold, mercury, antimony, lead, antimony and bismuth;

(3)向处于在500-800转/秒的转速的搅拌下的步骤(2)中得到的所述处于熔融状态的锂合金中加入多孔碳材料载体，继续搅拌20-40分钟，以得到所述锂合金-骨架碳复合材料。(3) adding a porous carbon material carrier to the lithium alloy in a molten state obtained in the step (2) at a stirring speed of 500-800 rpm, and stirring is continued for 20-40 minutes to obtain a Lithium alloy-skeletal carbon composite.

根据本发明的再一个方面，提供了一种用于锂电池的负极，其中所述负极的材料为如上所述的锂合金-骨架碳复合材料，或者所述负极的材料由如上所述的用于制备锂合金-骨架碳复合材料的方法制备。According to still another aspect of the present invention, there is provided a negative electrode for a lithium battery, wherein a material of the negative electrode is a lithium alloy-skeletal carbon composite material as described above, or a material of the negative electrode is used as described above Prepared by a method for preparing a lithium alloy-skeletal carbon composite.

根据本发明的又一个方面，提供了一种锂电池，所述锂电池包含如上所述的用于一次电池或二次电池的负极。According to still another aspect of the present invention, there is provided a lithium battery comprising the negative electrode for a primary battery or a secondary battery as described above.

与本领域中的现有技术相比，本发明的优点在于：通过在熔融锂中加入其它特定金属元素制备出锂合金，再将锂合金与骨架碳进行复合，能够形成具有较高载锂量的锂合金-骨架碳复合材料。该材料能够基本上保持骨架碳原有的形貌(例如，球形)，粒径为5-30微米。此外，金属锂在形成合金后其熔融状态下的表面能降低，从而更能容易的和骨架碳材料复合，从而提高骨架碳中的载锂量。Compared with the prior art in the art, the invention has the advantages that a lithium alloy is prepared by adding other specific metal elements to molten lithium, and then the lithium alloy is combined with the skeleton carbon to form a higher lithium loading capacity. Lithium alloy-skeletal carbon composite. The material is capable of substantially maintaining the original morphology of the framework carbon (e.g., spherical) with a particle size of 5-30 microns. In addition, the surface energy of the metallic lithium in the molten state after forming the alloy is lowered, so that it can be more easily combined with the skeleton carbon material, thereby increasing the amount of lithium supported in the skeleton carbon.

附图说明DRAWINGS

图1显示实施例1中制备的锂镁合金-骨架碳复合材料的放电曲线与根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料的放电曲线的比较；1 shows a comparison of a discharge curve of a lithium magnesium alloy-skeletal carbon composite prepared in Example 1 and a discharge curve of a metal lithium-skeletal carbon composite prepared according to the method of WO 2015139660 A1;

图2显示实施例1中制备的锂镁合金-骨架碳复合材料的扫描电子显微镜(SEM)照片以及EDS元素分析测试结果，其中：A为材料形貌的SEM图；B为复合材料中碳元素分布的EDS测试图；C为复合材料中镁元素分布的EDS测试图，并且以上图中的放大倍数为5000倍；2 shows a scanning electron microscope (SEM) photograph of the lithium magnesium alloy-skeletal carbon composite prepared in Example 1, and EDS elemental analysis test results, wherein: A is an SEM image of the material morphology; B is a carbon element in the composite material. Distributed EDS test chart; C is the EDS test chart of magnesium element distribution in the composite material, and the magnification in the above figure is 5000 times;

图3显示实施例1中制备的锂镁合金-骨架碳复合材料的恒流充放电测试结果与根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料的恒流充放电测试结果的比较；3 shows a comparison of the results of the constant current charge and discharge test of the lithium magnesium alloy-skeletal carbon composite prepared in Example 1 with the constant current charge and discharge test results of the metal lithium-skeletal carbon composite prepared according to the method of WO 2015139660 A1;

图4显示实施例2中制备的锂硅合金-骨架碳复合材料的放电曲线与根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料的放电曲线的比较；4 shows a comparison of a discharge curve of a lithium silicon alloy-skeletal carbon composite prepared in Example 2 with a discharge curve of a metal lithium-skeletal carbon composite prepared according to the method of WO 2015139660 A1;

图5显示实施例2中制备的锂硅合金-骨架碳复合材料的扫描电子显微镜(SEM)照片以及EDS元素分析测试结果，其中：A为材料形貌的SEM图； B为复合材料中碳元素分布的EDS测试图；C为复合材料中硅元素分布的EDS测试图，并且以上图中的放大倍数为5000倍；和5 shows a scanning electron microscope (SEM) photograph of a lithium silicon alloy-skeletal carbon composite prepared in Example 2, and an EDS elemental analysis test result, wherein: A is an SEM image of a material morphology; B is an EDS test chart of the distribution of carbon elements in the composite material; C is an EDS test chart of the distribution of silicon elements in the composite material, and the magnification in the above figure is 5000 times;

图6显示实施例2中制备的锂硅合金-骨架碳复合材料的恒流充放电测试结果与根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料的恒流充放电测试结果的比较。6 shows a comparison of the results of the constant current charge and discharge test of the lithium silicon alloy-skeletal carbon composite prepared in Example 2 with the constant current charge and discharge test results of the metal lithium-skeletal carbon composite prepared according to the method of WO 2015139660 A1.

具体实施方式Detailed ways

应当理解，在不脱离本公开的范围或精神的情况下，本领域技术人员能够根据本说明书的教导设想其他各种实施方案并能够对其进行修改。因此，以下的具体实施方式不具有限制性意义。It will be appreciated that those skilled in the art will be able to devise various other embodiments and modifications in accordance with the teachings of the present disclosure without departing from the scope and spirit of the disclosure. Therefore, the following specific embodiments are not limiting.

除非另外指明，否则本说明书和权利要求中使用的表示特征尺寸、数量和物化特性的所有数字均应该理解为在所有情况下均是由术语“约”来修饰的。因此，除非有相反的说明，否则上述说明书和所附权利要求书中列出的数值参数均是近似值，本领域的技术人员能够利用本文所公开的教导内容寻求获得的所需特性，适当改变这些近似值。用端点表示的数值范围的使用包括该范围内的所有数字以及该范围内的任何范围，例如，1至5包括1、1.1、1.3、1.5、2、2.75、3、3.80、4和5等等。All numbers expressing feature sizes, quantities, and physicochemical properties used in the specification and claims are to be understood as being modified in all instances by the term "about" unless otherwise indicated. Accordingly, the numerical parameters set forth in the above description and the appended claims are approximations, unless otherwise indicated, and those skilled in the art are able to utilize the teachings disclosed herein. approximation. The use of a range of values by endpoints includes all numbers in the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc. .

根据本发明的第一方面，提供了一种锂合金-骨架碳复合材料，所述锂合金-骨架碳复合材料包括多孔碳材料载体以及形成在所述多孔碳材料载体的表面上和孔隙内的锂合金。According to a first aspect of the present invention, there is provided a lithium alloy-skeletal carbon composite material comprising a porous carbon material support and formed on a surface of the porous carbon material support and in a pore Lithium alloy.

根据本发明的技术方案，所述锂合金处于熔融态时的表面能低于金属锂处于熔融态时的表面能。According to the technical solution of the present invention, the surface energy of the lithium alloy in a molten state is lower than the surface energy of the metallic lithium in a molten state.

根据本发明的技术方案，金属锂与某些特定元素在熔融状态下形成的锂合金具有较低的表面能，从而当将所述锂合金与骨架碳材料载体复合时，能够有效增加锂合金对骨架碳的浸润性，提高两者之间的亲和力，从而提高所得锂合金-骨架碳复合材料的载锂量和比容量。According to the technical solution of the present invention, the lithium alloy formed by the metal lithium and certain specific elements in a molten state has a lower surface energy, so that when the lithium alloy is combined with the skeleton carbon material carrier, the lithium alloy pair can be effectively increased. The wettability of the skeleton carbon increases the affinity between the two, thereby increasing the lithium loading capacity and specific capacity of the obtained lithium alloy-skeletal carbon composite.

根据本发明的某些技术方案，所述锂合金由由金属锂和选自镁、硅、硼、碳、氮、氧、氟、铝、磷、硫、氯、钙、锌、镓、锗、砷、硒、溴、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、铱、铂、金、汞、铊、铅、铋和钋中的一种或多种元素形成。优选地，所述元素为镁或硅。According to some aspects of the present invention, the lithium alloy is composed of lithium metal and is selected from the group consisting of magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, gallium, antimony, Formation of one or more elements of arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium, indium, tin, antimony, bismuth, iodine, antimony, platinum, gold, mercury, antimony, lead, antimony and bismuth . Preferably, the element is magnesium or silicon.

根据本发明的某些技术方案，根据本发明的锂合金包括锂的二元合金，例如锂镁合金、锂硅合金等。当所述锂合金由金属锂与另外一种元素形成时，锂合金中锂的重量百分比为70％～99.9％。当金属锂与所述另外一种金属元素的百分比控制在以上范围内时，可以有效增加锂合金对骨架碳的浸润性。According to some aspects of the present invention, a lithium alloy according to the present invention includes a binary alloy of lithium, For example, a lithium magnesium alloy, a lithium silicon alloy, or the like. When the lithium alloy is formed of metallic lithium and another element, the weight percentage of lithium in the lithium alloy is 70% to 99.9%. When the percentage of metallic lithium to the other metal element is controlled within the above range, the wettability of the lithium alloy to the skeleton carbon can be effectively increased.

根据本发明的某些技术方案，根据本发明的锂合金除以上所述的锂的二元合金以外，还包括锂的三元合金例如锂镁铝、锂金银三元合金，锂的四元合金例如锂镁铝锡、锂金银铂四元合金，等等。当所述锂合金由金属锂与另外多种元素形成时，在所述锂合金中，基于所述锂合金的总重量，所述另外多种元素的重量百分数为0.1-30重量％、优选10-25重量％、并且更优选10-15重量％。当所述另外多种元素的重量百分数被控制在以上范围内时，可以有效增加锂合金对骨架碳的浸润性。According to some aspects of the present invention, the lithium alloy according to the present invention includes a ternary alloy of lithium such as lithium magnesium aluminum, lithium gold silver ternary alloy, lithium ternary alloy in addition to the binary alloy of lithium described above. Alloys such as lithium magnesium aluminum tin, lithium gold silver platinum quaternary alloys, and the like. When the lithium alloy is formed of metallic lithium and a plurality of other elements, the weight percentage of the additional various elements is 0.1 to 30% by weight, preferably 10, based on the total weight of the lithium alloy. -25% by weight, and more preferably 10-15% by weight. When the weight percentage of the other various elements is controlled within the above range, the wettability of the lithium alloy to the skeleton carbon can be effectively increased.

根据本发明的某些技术方案，根据本发明的锂合金优选为锂镁合金或锂硅合金。According to some aspects of the invention, the lithium alloy according to the invention is preferably a lithium magnesium alloy or a lithium silicon alloy.

根据本发明，锂合金在熔融状态下对碳骨架具有增强的浸润性，从而增加载锂量。根据本发明的某些技术方案，基于所述锂合金-骨架碳复合材料的总重量，所述锂合金-骨架碳复合材料中的金属锂含量为45-95重量％、优选57-62重量％并且更优选59-61重量％。According to the present invention, the lithium alloy has enhanced wettability to the carbon skeleton in a molten state, thereby increasing the amount of lithium supported. According to some aspects of the present invention, the lithium metal content in the lithium alloy-skeletal carbon composite is 45 to 95% by weight, preferably 57 to 62% by weight, based on the total weight of the lithium alloy-skeletal carbon composite material. And more preferably 59-61% by weight.

根据本发明，锂合金在熔融状态下对碳骨架具有增强的浸润性，从而锂合金-骨架碳复合材料的增加载锂量，进而增加锂合金-骨架碳复合材料的比容量。根据本发明的某些技术方案，所述锂合金-骨架碳复合材料的比容量为1000-2800mAh/g,优选1000-2470mAh/g。其中，对于一次电池而言，锂合金-骨架碳复合材料的比容量优选为1000-1200mAh/g，并且对于二次电池而言，锂合金-骨架碳复合材料的比容量优选为2210-2385mAh/g并且更优选2272-2365mAh/g。According to the present invention, the lithium alloy has enhanced wettability to the carbon skeleton in a molten state, so that the lithium alloy-skeletal carbon composite increases the amount of lithium supported, thereby increasing the specific capacity of the lithium alloy-skeletal carbon composite. According to some aspects of the present invention, the lithium alloy-skeletal carbon composite has a specific capacity of 1000-2800 mAh/g, preferably 1000-2470 mAh/g. Wherein, for the primary battery, the specific capacity of the lithium alloy-skeletal carbon composite material is preferably 1000-1200 mAh/g, and for the secondary battery, the specific capacity of the lithium alloy-skeletal carbon composite material is preferably 2210-2385 mAh/ g and more preferably 2272-2365 mAh/g.

根据本发明的某些具体实施方案，在本发明中所采用的锂为电池级金属锂。该电池级金属锂购自天津中能锂业有限公司，纯度为99.9％。According to some embodiments of the invention, the lithium employed in the present invention is a battery grade metallic lithium. The battery grade lithium metal was purchased from Tianjin Zhongneng Lithium Industry Co., Ltd. with a purity of 99.9%.

根据本发明的某些具体实施方案，根据本发明的用于批量生产锂碳复合材料的方法中所采用的多孔碳材料载体选自下列各项中的一种或多种：碳纳米管微球、碳纤维微球、中间相碳微球、乙炔黑碳微球、科琴黑碳微球、Super-P微球、多孔活性炭微球、石墨微球、石墨烯微球等等。According to some embodiments of the present invention, the porous carbon material carrier used in the method for mass producing a lithium carbon composite according to the present invention is selected from one or more of the following: carbon nanotube microspheres , carbon fiber microspheres, mesocarbon microbeads, acetylene black carbon microspheres, Ketjen black carbon microspheres, Super-P microspheres, porous activated carbon microspheres, graphite microspheres, graphene microspheres, and the like.

优选地，所述多孔碳材料载体为碳纳米管微球。所述碳纳米管微球可以根据PCT国际申请公开号WO 2015139660A1和中国专利申请号CN 201410395114.0中公开的制备方法制备。所述碳纳米管微球具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。优选地，所述碳纳米管微球的平均直径为1μm至100μm；和/或所述碳纳米管微球的电导率为1×10^-3至10³S·cm^-1；和/或所述碳纳米管微球的最大可承受压力为20MPa；和/或所述碳纳米管微球的比表面积为100至1500m²/g；和/或所述碳纳米管微球所含孔隙的孔径为1nm至200nm。Preferably, the porous carbon material carrier is carbon nanotube microspheres. The carbon nanotube microspheres can be prepared according to the preparation methods disclosed in PCT International Application Publication No. WO 2015139660 A1 and Chinese Patent Application No. CN 201410395114.0. The carbon nanotube microspheres have any one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spherical-like aggregate structure, a porous spherical aggregate structure, and a doughnut-shaped aggregate structure. Preferably, the carbon nanotube microspheres have an average diameter of from 1 μm to 100 μm; and/or the carbon nanotube microspheres have an electrical conductivity of from 1×10 ⁻³ to 10 ³ S·cm ⁻¹ ; and/or The maximum allowable pressure of the carbon nanotube microspheres is 20 MPa; and/or the specific surface area of the carbon nanotube microspheres is 100 to 1500 m ² /g; and/or the pore diameter of the carbon nanotube microspheres It is from 1 nm to 200 nm.

根据本发明的某些具体实施方案，所述碳纳米管包括多壁碳纳米管、双壁碳纳米管和单壁碳纳米管中的任意一种或两种以上的组合。According to some embodiments of the present invention, the carbon nanotubes include any one or a combination of two or more of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes.

根据本发明的另一个方面，提供一种用于制备锂合金-骨架碳复合材料的方法，所述方法包括在惰性气氛下依次进行下列步骤：According to another aspect of the present invention, there is provided a method for producing a lithium alloy-skeletal carbon composite, the method comprising sequentially performing the following steps under an inert atmosphere:

(1)将金属锂加热到锂的熔融温度(180-220℃)，以得到熔融锂；(1) heating lithium metal to a melting temperature of lithium (180-220 ° C) to obtain molten lithium;

(2)在500-800转/秒的转速的搅拌下，将步骤(1)中得到的熔融锂升温至220-1000℃，加入一种或多种元素熔炼得到熔融状态的锂合金，加入的所述元素选自镁、硅、硼、碳、氮、氧、氟、铝、磷、硫、氯、钙、锌、镓、锗、砷、硒、溴、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、铱、铂、金、汞、铊、铅、铋和钋中的一种或多种；(2) heating the molten lithium obtained in the step (1) to 220-1000 ° C under stirring at a rotation speed of 500-800 rpm, adding one or more elements to obtain a molten lithium alloy, and adding The element is selected from the group consisting of magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, gallium, antimony, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium. , one or more of indium, tin, antimony, bismuth, iodine, antimony, platinum, gold, mercury, antimony, lead, antimony and bismuth;

根据本发明的某些技术方案，所述锂合金由金属锂和选自镁、硅、硼、碳、氮、氧、氟、铝、磷、硫、氯、钙、锌、镓、锗、砷、硒、溴、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、铱、铂、金、汞、铊、铅、铋和钋中的一种或多种元素形成。优选地，所述元素或镁或硅。According to some aspects of the present invention, the lithium alloy is composed of lithium metal and is selected from the group consisting of magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, gallium, antimony, and arsenic. Forming one or more elements of selenium, bromine, antimony, bismuth, palladium, silver, cadmium, indium, tin, antimony, bismuth, iodine, antimony, platinum, gold, mercury, antimony, lead, antimony and bismuth. Preferably, the element is either magnesium or silicon.

根据本发明的某些技术方案，根据本发明的锂合金包括锂的二元合金，例如锂镁合金、锂硅合金等。锂合金中锂的重量百分比为70％至99.9％。当金属锂与所述另外一种金属元素的百分比控制在以上范围内时，可以有效增加锂合金对骨架碳的浸润性。According to some aspects of the present invention, the lithium alloy according to the present invention includes a binary alloy of lithium, such as a lithium magnesium alloy, a lithium silicon alloy, or the like. The weight percentage of lithium in the lithium alloy is 70% to 99.9%. When the percentage of metallic lithium and the other metal element is controlled within the above range, it can be effectively increased The infiltration of the lithium alloy with the framework carbon.

根据本发明的某些技术方案，根据本发明的锂合金除以上所述的锂的二元合金以外，还包括锂的三元合金例如锂金银三元合金，锂的四元合金例如锂金银铂四元合金，等等。当所述锂合金由金属锂与另外多种元素形成时，在所述锂合金中，基于所述锂合金的总重量，所述另外多种元素的投料重量百分数为0.1-30重量％、优选10-25重量％、并且更优选10-15重量％。当所述另外多种元素的投料重量百分数被控制在以上范围内时，可以有效增加锂合金对骨架碳的浸润性。According to some aspects of the present invention, the lithium alloy according to the present invention includes, in addition to the binary alloy of lithium described above, a ternary alloy of lithium such as a lithium gold silver ternary alloy, a quaternary alloy of lithium such as lithium gold. Silver platinum quaternary alloy, and so on. When the lithium alloy is formed of metallic lithium and a plurality of other elements, in the lithium alloy, the weight ratio of the additional various elements is 0.1 to 30% by weight, based on the total weight of the lithium alloy, preferably 10-25% by weight, and more preferably 10-15% by weight. When the weight percentage of the feed of the other various elements is controlled within the above range, the wettability of the lithium alloy to the skeleton carbon can be effectively increased.

根据本发明，锂合金在熔融状态下对碳骨架具有增强的浸润性，从而锂合金-骨架碳复合材料的增加载锂量，进而增加锂合金-骨架碳复合材料的比容量。根据本发明的某些技术方案，所述锂合金-骨架碳复合材料的比容量为1000-2800mAh/g，优选1000-2470mAh/g。其中，对于一次电池而言，锂合金-骨架碳复合材料的比容量优选为1000-1200mAh/g，并且对于二次电池而言，锂合金-骨架碳复合材料的比容量优选为优选2210-2385mAh/g并且更优选2272-2365mAh/g。According to the present invention, the lithium alloy has enhanced wettability to the carbon skeleton in a molten state, so that the lithium alloy-skeletal carbon composite increases the amount of lithium supported, thereby increasing the specific capacity of the lithium alloy-skeletal carbon composite. According to some aspects of the present invention, the lithium alloy-skeletal carbon composite has a specific capacity of 1000-2800 mAh/g, preferably 1000-2470 mAh/g. Wherein, for the primary battery, the specific capacity of the lithium alloy-skeletal carbon composite material is preferably 1000-1200 mAh/g, and for the secondary battery, the specific capacity of the lithium alloy-skeletal carbon composite material is preferably 2210-2385 mAh. /g and more preferably 2272-2365 mAh/g.

优选地，所述多孔碳材料载体为碳纳米管微球。所述碳纳米管微球可以根据PCT国际申请公开号WO 2015139660A1和中国专利申请号CN 201410395114.0中公开的制备方法制备。所述碳纳米管微球具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。优选地，所述碳纳米管微球的平均直径为1μm至100μm；和/或所述碳纳米管微球的电导率为1×10^-3至10³S·cm^-1；和/或所述碳纳米管微球的最大可承受压力为20MPa；和/或所述碳纳米管微球的比表面积为100至1500m²/g；和/或所述碳纳米管微球所含孔隙的孔径为1nm至200nm。Preferably, the porous carbon material carrier is carbon nanotube microspheres. The carbon nanotube microspheres can be prepared according to the preparation methods disclosed in PCT International Application Publication No. WO 2015139660 A1 and Chinese Patent Application No. CN 201410395114.0. The carbon nanotube microspheres have any one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spherical aggregate structure, a porous spherical aggregate structure, and a doughnut aggregate structure. Preferably, the carbon nanotube microspheres have an average diameter of from 1 μm to 100 μm; and/or the carbon nanotube microspheres have an electrical conductivity of from 1×10 ⁻³ to 10 ³ S·cm ⁻¹ ; and/or The maximum allowable pressure of the carbon nanotube microspheres is 20 MPa; and/or the specific surface area of the carbon nanotube microspheres is 100 to 1500 m ² /g; and/or the pore diameter of the carbon nanotube microspheres It is from 1 nm to 200 nm.

根据本发明的再一个方面，提供一种用于锂电池的负极，其中所述负极的材料为如上所述的锂合金-骨架碳复合材料，或者所述负极的材料由如上所述的用于制备锂合金-骨架碳复合材料的方法制备。According to still another aspect of the present invention, there is provided a negative electrode for a lithium battery, wherein a material of the negative electrode is a lithium alloy-skeletal carbon composite material as described above, or a material of the negative electrode is used as described above Preparation of a method for preparing a lithium alloy-skeletal carbon composite.

根据本发明的又一个方面，提供一种锂电池，所述锂电池包含如上所述的用于一次电池或二次电池的负极。优选地，所述一次电池为锂热电池，所述二次电池为金属锂-氧化物电池、金属锂-聚合物电池或可充电锂离子电池。According to still another aspect of the present invention, there is provided a lithium battery comprising the negative electrode for a primary battery or a secondary battery as described above. Preferably, the primary battery is a lithium thermal battery, and the secondary battery is a metal lithium-oxide battery, a metal lithium-polymer battery or a rechargeable lithium ion battery.

下列具体实施方式意在示例性地而非限定性地说明本公开。The following detailed description is intended to be illustrative, and not restrictive.

具体实施方式1是一种锂合金-骨架碳复合材料，所述锂合金-骨架碳复合材料包括多孔碳材料载体以及形成在所述多孔碳材料载体的表面上和孔隙内的锂合金。1 is a lithium alloy-skeletal carbon composite material comprising a porous carbon material support and a lithium alloy formed on the surface of the porous carbon material support and in the pores.

具体实施方式2是根据具体实施方式1所述的锂合金-骨架碳复合材料，其中所述锂合金由金属锂和选自镁、硅、硼、碳、氮、氧、氟、铝、磷、硫、氯、钙、锌、镓、锗、砷、硒、溴、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、铱、铂、金、汞、铊、铅、铋和钋中的一种或多种元素形成。Embodiment 2 is the lithium alloy-skeletal carbon composite material according to Embodiment 1, wherein the lithium alloy is composed of lithium metal and selected from the group consisting of magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, Sulfur, chlorine, calcium, zinc, gallium, antimony, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium, indium, tin, antimony, bismuth, iodine, antimony, platinum, gold, mercury, antimony, lead, One or more elements of bismuth and strontium are formed.

具体实施方式3是根据具体实施方式2所述的锂合金-骨架碳复合材料，其中当所述锂合金由金属锂与另外一种元素形成时，锂合金中锂的重量百分比为70％～99.9％。The third embodiment is the lithium alloy-skeletal carbon composite material according to the second embodiment, wherein when the lithium alloy is formed of metallic lithium and another element, the weight percentage of lithium in the lithium alloy is 70% to 99.9. %.

具体实施方式4是根据具体实施方式2所述的锂合金-骨架碳复合材料，其中当所述锂合金由金属锂与另外多种元素形成时，在所述锂合金中，基于所述锂合金的总重量，所述另外多种元素的重量百分数为0.1-30重量％。Embodiment 4 is the lithium alloy-skeletal carbon composite material according to Embodiment 2, wherein when the lithium alloy is formed of metallic lithium and a plurality of other elements, in the lithium alloy, based on the lithium alloy The total weight of the additional various elements is from 0.1 to 30% by weight.

具体实施方式5是根据具体实施方式2所述的锂合金-骨架碳复合材料，其中所述锂合金为锂镁合金、锂硅合金、锂铝合金、锂硼合金以及其他多元衍生物。The fifth embodiment is the lithium alloy-skeletal carbon composite material according to the second embodiment, wherein the lithium alloy is a lithium magnesium alloy, a lithium silicon alloy, a lithium aluminum alloy, a lithium boron alloy, and other plural derivative.

具体实施方式6是根据具体实施方式1所述的锂合金-骨架碳复合材料，其中基于所述锂合金-骨架碳复合材料的总重量，所述锂合金-骨架碳复合材料中的金属锂含量为45-95重量％。Embodiment 6 is the lithium alloy-skeletal carbon composite material according to Embodiment 1, wherein the lithium metal content in the lithium alloy-skeletal carbon composite material is based on the total weight of the lithium alloy-skeletal carbon composite material. It is 45-95% by weight.

具体实施方式7是根据具体实施方式1所述的锂合金-骨架碳复合材料，其中所述锂合金-骨架碳复合材料的比容量为1000-2800mAh/g。The seventh embodiment is the lithium alloy-skeletal carbon composite material according to the first embodiment, wherein the lithium alloy-skeletal carbon composite material has a specific capacity of 1000-2800 mAh/g.

具体实施方式8是根据具体实施方式1所述的锂合金-骨架碳复合材料，其中所述多孔碳材料载体选自下列各项中的一种或多种：碳纳米管微球、碳纤维微球、中间相碳微球、乙炔黑碳微球、科琴黑碳微球、Super-P微球、多孔活性炭微球、石墨微球和石墨烯微球。The lithium alloy-skeletal carbon composite material according to the first embodiment, wherein the porous carbon material carrier is one or more selected from the group consisting of carbon nanotube microspheres and carbon fiber microspheres. , mesophase carbon microspheres, acetylene black carbon microspheres, Ketjen black carbon microspheres, Super-P microspheres, porous activated carbon microspheres, graphite microspheres and graphene microspheres.

具体实施方式9是根据具体实施方式1所述的锂合金-骨架碳复合材料，其中所述多孔碳材料载体为碳纳米管微球。Embodiment 9 is the lithium alloy-skeletal carbon composite material according to Embodiment 1, wherein the porous carbon material carrier is carbon nanotube microspheres.

具体实施方式10是根据具体实施方式9所述的锂合金-骨架碳复合材料，其中所述碳纳米管微球具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。10 is a lithium alloy-skeletal carbon composite material according to a specific embodiment 9, wherein the carbon nanotube microspheres have a microspherical solid aggregate structure, a spherical aggregate structure, a spheroidal aggregate structure, a porous spherical aggregate structure, and Any of the doughnut-shaped aggregate structures.

具体实施方式11是根据具体实施方式9所述的锂合金-骨架碳复合材料，其中：Embodiment 11 is the lithium alloy-skeletal carbon composite material according to Embodiment 9, wherein:

所述碳纳米管微球的平均直径为1μm至100μm；和/或The carbon nanotube microspheres have an average diameter of from 1 μm to 100 μm; and/or

所述碳纳米管微球的电导率为1×10^-3至10³S·cm^-1；和/或The carbon nanotube microspheres have a conductivity of 1×10 ⁻³ to 10 ³ S·cm ^-1 ; and/or

所述碳纳米管微球的最大可承受压力为20MPa；和/或The maximum compressive pressure of the carbon nanotube microspheres is 20 MPa; and/or

所述碳纳米管微球的比表面积为100至1500m²/g；和/或The carbon nanotube microspheres have a specific surface area of 100 to 1500 m ² /g; and/or

所述碳纳米管微球所含孔隙的孔径为1nm至200nm。The pores of the carbon nanotube microspheres have a pore diameter of from 1 nm to 200 nm.

具体实施方式12是根据具体实施方式9所述的锂合金-骨架碳复合材料，其中所述碳纳米管包括多壁碳纳米管、双壁碳纳米管和单壁碳纳米管中的任意一种或两种以上的组合。Embodiment 12 is the lithium alloy-skeletal carbon composite material according to Embodiment 9, wherein the carbon nanotubes comprise any one of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes. Or a combination of two or more.

具体实施方式13是一种用于制备锂合金-骨架碳复合材料的方法，所述方法包括在惰性气氛下依次进行下列步骤：DETAILED DESCRIPTION 13 is a method for preparing a lithium alloy-skeletal carbon composite, the method comprising sequentially performing the following steps under an inert atmosphere:

(2)在500-800转/秒的转速的搅拌下，将步骤(1)中得到的熔融锂升温至220-1000℃，加入一种或多种元素熔炼得到熔融状态的锂合金，加入的所述元素选自镁、硅、硼、碳、氮、氧、氟、铝、磷、硫、氯、钙、锌、镓、锗、砷、硒、溴、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、铱、铂、金、汞、铊、铅、铋和钋中的一种或多种；(2) heating the molten lithium obtained in the step (1) to 220-1000 ° C under stirring at a rotation speed of 500-800 rpm, adding one or more elements to obtain a molten lithium alloy, and adding The element is selected from the group consisting of magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, One of gallium, germanium, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium, indium, tin, antimony, bismuth, iodine, antimony, platinum, gold, mercury, antimony, lead, antimony and antimony Multiple

具体实施方式14是根据具体实施方式13所述用于制备锂合金-骨架碳复合材料的方法，其中当所述锂合金由金属锂与另外一种元素形成时，所述的锂合金中锂的重量百分比为70％至99.9％。Embodiment 14 is the method for producing a lithium alloy-skeletal carbon composite according to Embodiment 13, wherein when the lithium alloy is formed of metallic lithium and another element, lithium in the lithium alloy The weight percentage is 70% to 99.9%.

具体实施方式15是根据具体实施方式13所述用于制备锂合金-骨架碳复合材料的方法，其中当由金属锂与另外多种元素形成所述锂合金时，基于所述锂合金的总重量，所述另外多种元素的投料重量百分数为0.1-30重量％。Embodiment 15 is the method for producing a lithium alloy-skeletal carbon composite according to Embodiment 13, wherein when the lithium alloy is formed of metallic lithium and a plurality of other elements, based on the total weight of the lithium alloy The additional plurality of elements are charged in a weight percentage of from 0.1 to 30% by weight.

具体实施方式16是根据具体实施方式13所述用于制备锂合金-骨架碳复合材料的方法，其中所述锂合金为锂镁合金、锂硅合金、锂铝合金、锂硼合金以及其他多元衍生物。Embodiment 16 is the method for preparing a lithium alloy-skeletal carbon composite according to Embodiment 13, wherein the lithium alloy is a lithium magnesium alloy, a lithium silicon alloy, a lithium aluminum alloy, a lithium boron alloy, and other multi-components. Things.

具体实施方式17是根据具体实施方式13所述用于制备锂合金-骨架碳复合材料的方法，其中基于所述锂合金-骨架碳复合材料的总重量，所述锂合金-骨架碳复合材料中的金属锂含量为45-95重量％。Embodiment 17 is the method for producing a lithium alloy-skeletal carbon composite according to Embodiment 13, wherein the lithium alloy-skeletal carbon composite is based on the total weight of the lithium alloy-skeletal carbon composite. The metal lithium content is from 45 to 95% by weight.

具体实施方式18是根据具体实施方式13所述用于制备锂合金-骨架碳复合材料的方法，其中所述锂合金-骨架碳复合材料的比容量为1000-2800mAh/g。Embodiment 18 is the method for producing a lithium alloy-skeletal carbon composite according to Embodiment 13, wherein the lithium alloy-skeletal carbon composite has a specific capacity of 1000-2800 mAh/g.

具体实施方式19是根据具体实施方式13所述用于制备锂合金-骨架碳复合材料的方法，其中所述多孔碳材料载体选自下列各项中的一种或多种：碳纳米管微球、碳纤维微球、中间相碳微球、乙炔黑碳微球、科琴黑碳微球、Super-P微球、多孔活性炭微球、石墨微球和石墨烯微球。Embodiment 19 is the method for producing a lithium alloy-skeletal carbon composite according to Embodiment 13, wherein the porous carbon material carrier is selected from one or more of the following: carbon nanotube microspheres , carbon fiber microspheres, mesocarbon microbeads, acetylene black carbon microspheres, Ketjen black carbon microspheres, Super-P microspheres, porous activated carbon microspheres, graphite microspheres and graphene microspheres.

具体实施方式20是根据具体实施方式13所述用于制备锂合金-骨架碳复合材料的方法，其中所述多孔碳材料载体为碳纳米管微球。Embodiment 20 is the method for producing a lithium alloy-skeletal carbon composite according to Embodiment 13, wherein the porous carbon material carrier is carbon nanotube microspheres.

具体实施方式21是根据具体实施方式20所述用于制备锂合金-骨架碳复合材料的方法，其中所述碳纳米管微球具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。 21 is a method for preparing a lithium alloy-skeletal carbon composite according to Embodiment 20, wherein the carbon nanotube microspheres have a microspherical solid aggregate structure, a spherical aggregate structure, a spherical aggregate structure, and a porous Any of a spherical aggregate structure and a doughnut-shaped aggregate structure.

具体实施方式22是根据具体实施方式20所述用于制备锂合金-骨架碳复合材料的方法，其中：Embodiment 22 is a method for preparing a lithium alloy-skeletal carbon composite according to Embodiment 20, wherein:

具体实施方式23是根据具体实施方式20所述用于制备锂合金-骨架碳复合材料的方法，其中所述碳纳米管包括多壁碳纳米管、双壁碳纳米管和单壁碳纳米管中的任意一种或两种以上的组合。Embodiment 23 is the method for preparing a lithium alloy-skeletal carbon composite according to Embodiment 20, wherein the carbon nanotubes comprise multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes. Any one or a combination of two or more.

具体实施方式24是一种用于锂电池的负极，其中所述负极的材料为根据具体实施方式1至12中任一项所述的锂合金-骨架碳复合材料，或者所述负极的材料由根据具体实施方式13至23中任一项所述的用于制备锂合金-骨架碳复合材料的方法制备。The embodiment 24 is a negative electrode for a lithium battery, wherein the material of the negative electrode is the lithium alloy-skeletal carbon composite according to any one of the embodiments 1 to 12, or the material of the negative electrode is The method for producing a lithium alloy-skeletal carbon composite material according to any one of the embodiments 13 to 23 is prepared.

具体实施方式25是一种锂电池，所述锂电池包含根据具体实施方式24所述的用于锂电池的负极。Embodiment 25 is a lithium battery including the negative electrode for a lithium battery according to Embodiment 24.

具体实施方式26是根据具体实施方式25所述的锂电池，所述的锂电池包括二次电池(如金属锂-氧化物电池、金属锂-聚合物电池或可充电锂离子电池)和一次电池(如锂热电池)。The embodiment 26 is the lithium battery according to the embodiment 25, wherein the lithium battery comprises a secondary battery (such as a metal lithium-oxide battery, a metal lithium-polymer battery or a rechargeable lithium ion battery), and a primary battery. (such as lithium battery).

下面结合实施例对本发明进行更详细的描述。需要指出，这些描述和实施例都是为了使本发明便于理解，而非对本发明的限制。本发明的保护范围以所附的权利要求书为准。The invention will now be described in greater detail with reference to the embodiments. It is to be understood that the description and examples are intended to be illustrative and not restrictive. The scope of the invention is defined by the appended claims.

实施例Example

在本发明中，所提及的“％”为“重量％”，并且所提及的“份”为“重量份”。In the present invention, the "%" mentioned is "% by weight", and the "parts" referred to are "parts by weight".

测试方法Test Methods

在本公开内容中，对得到的各种锂合金-骨架碳复合材料关于载锂量、比容量、形貌和拔锂镀锂循环性能等方面进行了测试，具体测试方法描述如下。In the present disclosure, various lithium alloy-skeletal carbon composite materials obtained are tested in terms of lithium loading capacity, specific capacity, morphology, and lithium plating lithium plating cycle performance, and specific test methods are described as follows. under.

载锂量Lithium loading

称量m克所制备的锂合金-骨架碳复合材料或金属锂-骨架碳复合材料并且将其压制在直径为1.5cm的泡沫铜上，作为负极。将所述负极与作为正极的金属锂片组装成模拟电池，其中所采用的电解液为LiPF₆溶解在体积比1:1:1的碳酸乙烯酯(EC)、二甲基碳酸酯(DMC)和碳酸甲乙酯(EMC)的混合溶剂中所得的溶液。将所述模拟电池以0.1mA的电流持续放电，直至电压值为1V停止放电，该过程放电的容量为Q(容量的电位为库伦)。根据如下公式计算锂碳复合材料中的载锂量：0.5 g of the prepared lithium alloy-skeletal carbon composite material or metallic lithium-skeletal carbon composite material was weighed and pressed on a foamed copper having a diameter of 1.5 cm as a negative electrode. The negative electrode and the lithium metal sheet as a positive electrode were assembled into a simulated battery, wherein the electrolyte used was a solution of LiPF ₆ dissolved in ethylene carbonate (EC), dimethyl carbonate (DMC) at a volume ratio of 1:1:1. A solution obtained in a mixed solvent with ethyl methyl carbonate (EMC). The analog battery was continuously discharged at a current of 0.1 mA until the voltage value was 1 V to stop the discharge, and the discharge capacity of the process was Q (the potential of the capacity was Coulomb). Calculate the amount of lithium in the lithium carbon composite according to the following formula:

形貌Morphology

通过扫描电子显微镜(SEM)(日本日立公司生产的型号为S4800的冷场发射扫描电子显微镜)观察金属锂-多孔碳复合材料的形貌，并且通过扫描电子显微照片统计颗粒的粒径分布。另外，利用所述扫描电子显微镜(SEM)对金属锂-多孔碳复合材料进行EDS元素分析。The morphology of the lithium metal-porous carbon composite was observed by a scanning electron microscope (SEM) (S4800 cold field emission scanning electron microscope manufactured by Hitachi, Ltd.), and the particle size distribution of the particles was counted by scanning electron micrograph. Further, the metal lithium-porous carbon composite material was subjected to EDS elemental analysis by the scanning electron microscope (SEM).

拔锂镀锂循环Lithium plating lithium cycle

称量m克所制备的锂合金-骨架碳复合材料或金属锂-骨架碳复合材料并且将其压制在直径为1.5cm的泡沫铜上，作为负极。将所述负极与作为正极的金属锂片组装成模拟电池，其中所采用的电解液为LiPF₆溶解在体积比1:1:1的碳酸乙烯酯(EC)、二甲基碳酸酯(DMC)和碳酸甲乙酯(EMC)的混合溶剂中所得的溶液。将得到的模拟电池在电池测试仪(深圳市新威尔有限公司生产的型号为CT-3008的电池测试仪)上搁置360分钟，其中以1mA电流恒流充电(镀锂)1小时，再以1mA电流恒流放电(拔锂)1小时，循环充电放电过程200次。0.5 g of the prepared lithium alloy-skeletal carbon composite material or metallic lithium-skeletal carbon composite material was weighed and pressed on a foamed copper having a diameter of 1.5 cm as a negative electrode. The negative electrode and the lithium metal sheet as a positive electrode were assembled into a simulated battery, wherein the electrolyte used was a solution of LiPF ₆ dissolved in ethylene carbonate (EC), dimethyl carbonate (DMC) at a volume ratio of 1:1:1. A solution obtained in a mixed solvent with ethyl methyl carbonate (EMC). The obtained analog battery was placed on a battery tester (a battery tester model CT-3008 manufactured by Shenzhen Xinwei Co., Ltd.) for 360 minutes, in which a constant current was charged at 1 mA (lithium plating) for 1 hour, and then 1 mA current constant current discharge (pulled lithium) for 1 hour, cycle charge and discharge process 200 times.

实施例1Example 1

根据PCT国际申请公开号WO 2015139660A1和中国专利申请号CN 201410395114.0中公开的制备方法制备碳纳米管微球。所得到的碳纳米管微球具有球形聚集结构，其中所述碳纳米管微球的平均直径为5μm，电导率为10S·cm^-1，最大可承受压力为20MPa，比表面积为255m²/g，并且所述碳纳米管微球所含孔隙的孔径为20nm至100nm。Carbon nanotube microspheres are prepared according to the preparation methods disclosed in PCT International Application Publication No. WO 2015139660 A1 and Chinese Patent Application No. CN 201410395114.0. The obtained carbon nanotube microspheres have a spherical aggregate structure, wherein the carbon nanotube microspheres have an average diameter of 5 μm, an electric conductivity of 10 S·cm ^-1 , a maximum withstand pressure of 20 MPa, and a specific surface area of 255 m ² /g. And the pores of the carbon nanotube microspheres have a pore diameter of 20 nm to 100 nm.

在惰性气氛下，将9g金属锂加热到220℃以使其熔融。向处于在800转/秒的转速的搅拌下的熔融的锂中加入1g金属镁，继续搅拌20分钟，冷却后得到10重量％的镁含量的锂镁合金。将10g的所述锂镁合金加热至其熔融状态，并且向处于800转/秒的转速的搅拌下的熔融的锂镁合金中加入5g以上步骤中所得的碳纳米管微球，继续搅拌40分钟，待产物冷却后得到锂镁合金-骨架碳复合材料。根据以上所述的计算载锂量的方法通过计算可知该锂镁合金-骨架碳复合材料的载锂量为64重量％。9 g of metallic lithium was heated to 220 ° C under an inert atmosphere to melt it. To the molten lithium at a stirring speed of 800 rpm, 1 g of metallic magnesium was added, stirring was continued for 20 minutes, and after cooling, a magnesium-magnesium alloy having a magnesium content of 10% by weight was obtained. 10 g of the lithium magnesium alloy was heated to its molten state, and 5 g of the carbon nanotube microspheres obtained in the above step was added to the molten lithium magnesium alloy under stirring at 800 rpm, and stirring was continued for 40 minutes. After the product is cooled, a lithium magnesium alloy-skeletal carbon composite material is obtained. According to the above method for calculating the amount of lithium supported, the lithium-loading amount of the lithium-magnesium alloy-skeletal carbon composite material was found to be 64% by weight.

分别地，根据WO 2015139660A1中的方法,将10g金属锂加热到180℃以使其熔融，并且向熔融的锂中加入5g以上步骤中所得的碳纳米管微球，继续搅拌40分钟，待产物冷却后得到锂-骨架碳复合材料。根据以上所述的计算载锂量的方法通过计算可知该锂-骨架碳复合材料的载锂量为载锂量为53重量％。Separately, according to the method in WO 2015139660 A1, 10 g of metallic lithium is heated to 180 ° C to melt it, and 5 g of the carbon nanotube microspheres obtained in the above step are added to the molten lithium, stirring is continued for 40 minutes, and the product is cooled. A lithium-skeletal carbon composite is obtained. According to the above method for calculating the amount of lithium supported, the lithium-supporting amount of the lithium-skeletal carbon composite material was found to be 53% by weight of lithium.

根据以上测试方法部分中关于形貌和拔锂镀锂循环性能等方面所描述的方法，对以上得到的锂镁合金-骨架碳复合材料的形貌和拔锂镀锂循环性能进行测试，并且对以上得到的锂-骨架碳复合材料的拔锂镀锂循环性能进行测试。图1显示实施例1中制备的锂镁合金-骨架碳复合材料的放电曲线与根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料的放电曲线的比较。由于熔融态的金属锂和金属镁混合形成的锂镁合金降低了熔融态金属锂表面能，使得熔融态金属锂更容易进入骨架碳材料的内部，因此锂镁合金-骨架碳复合负极比金属锂-骨架碳材料具有更高的比容量。图2显示实施例1中制备的锂镁合金-骨架碳复合材料的扫描电子显微镜(SEM)照片以及EDS元素分析测试结果，其中：A为材料形貌的SEM图；B为复合材料中碳元素分布的EDS测试图；C为复合材料中Mg分布的EDS测试图，并且以上图中的放大倍数为5000倍。由图2(A)可知，所得到的锂镁合金-骨架碳复合材料基本上保持了作为载体的多孔碳材料载体的球形形状。此外，从图2(B)和(C)的比较可知，金属镁的分布与碳分布基本吻合，说明金属镁均匀地分布在骨架碳的表面和孔隙内。图3显示实施例1中制备的锂镁合金-骨架碳复合材料的恒流充放电测试结果与根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料的恒流充放电测试结果的比较。从该图可以看出，锂镁合金-骨架碳复合材料在开始时极化电压很小，表明材料具有大的比表面积，能极大地降低电流密度，有效抑制锂枝晶的生成。并且由于合金中镁的存在，在材料内部起到促进金属锂沉积的作用，因此该材料比根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料具有了更加出色的循环稳定性。According to the method described in the above test method section on the morphology and lithium plating lithium cycle performance, the morphology of the lithium-magnesium alloy-skeletal carbon composite obtained above and the lithium plating lithium plating cycle performance were tested, and The lithium-plated carbon composite material obtained above was tested for lithium plating cycle performance. 1 shows a comparison of a discharge curve of a lithium magnesium alloy-skeletal carbon composite prepared in Example 1 with a discharge curve of a metal lithium-skeletal carbon composite prepared according to the method of WO 2015139660 A1. The lithium-magnesium alloy formed by the mixing of the molten metal lithium and the metal magnesium reduces the surface energy of the molten metal lithium, so that the molten metal lithium is more likely to enter the interior of the skeleton carbon material, so the lithium magnesium alloy-skeletal carbon composite anode is more than the metal lithium - Skeletal carbon materials have a higher specific capacity. 2 shows a scanning electron microscope (SEM) photograph of the lithium magnesium alloy-skeletal carbon composite prepared in Example 1, and EDS elemental analysis test results, wherein: A is an SEM image of the material morphology; B is a carbon element in the composite material. The distributed EDS test chart; C is the EDS test chart of the Mg distribution in the composite material, and the magnification in the above figure is 5000 times. As is apparent from Fig. 2(A), the obtained lithium magnesium alloy-skeletal carbon composite material substantially maintains the spherical shape of the porous carbon material carrier as a carrier. In addition, as can be seen from the comparison of FIGS. 2(B) and (C), the distribution of metallic magnesium is substantially consistent with the carbon distribution, indicating that the metallic magnesium is uniformly distributed in the surface and pores of the framework carbon. Figure 3 shows the lithium magnesium alloy prepared in Example 1. The results of the constant current charge and discharge test results of the gold-skeletal carbon composite material and the constant current charge and discharge test results of the metal lithium-skeletal carbon composite material prepared according to the method of WO 2015139660A1. It can be seen from the figure that the lithium-magnesium alloy-skeletal carbon composite material has a small polarization voltage at the beginning, indicating that the material has a large specific surface area, which can greatly reduce the current density and effectively inhibit the formation of lithium dendrites. And because of the presence of magnesium in the alloy, it promotes the deposition of metallic lithium inside the material, so the material has more excellent cycle stability than the metallic lithium-skeletal carbon composite prepared according to the method of WO 2015139660A1.

实施例2Example 2

在惰性气氛下，将9g金属锂加热到220℃以使其熔融。向处于在500转/秒的转速的搅拌下的熔融的锂中加入1g金属硅，升温至600℃，继续搅拌20分钟，冷却后得到10重量％的硅含量的锂硅合金。将10g的所述锂硅合金加热至其熔融状态，并且向处于在500转/秒的转速的搅拌下的熔融的锂硅合金中加入5g以上步骤中所得的碳纳米管微球，继续搅拌40分钟，待产物冷却后得到锂硅合金-骨架碳复合材料。根据以上所述的计算载锂量的方法通过计算可知该锂硅合金-骨架碳复合材料的载锂量为57重量％。9 g of metallic lithium was heated to 220 ° C under an inert atmosphere to melt it. 1 g of metal silicon was added to the molten lithium at a stirring speed of 500 rpm, and the temperature was raised to 600 ° C, stirring was continued for 20 minutes, and after cooling, a lithium silicon alloy having a silicon content of 10% by weight was obtained. 10 g of the lithium silicon alloy was heated to its molten state, and 5 g of the carbon nanotube microspheres obtained in the above step was added to the molten lithium silicon alloy at a stirring speed of 500 rpm, and stirring was continued 40. Minutes, after the product was cooled, a lithium silicon alloy-skeletal carbon composite was obtained. According to the above method for calculating the amount of lithium supported, the lithium-loaded amount of the lithium silicon alloy-skeletal carbon composite material was 57% by weight.

根据以上测试方法部分中关于形貌和拔锂镀锂循环性能等方面所描述的方法，对以上得到的锂硅合金-骨架碳复合材料的形貌和拔锂镀锂循环性能进行测试，并且对以上得到的锂-骨架碳复合材料的拔锂镀锂循环性能进行测试。图4显示实施例2中制备的锂硅合金-骨架碳复合材料的放电曲线与根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料的放电曲线的比较。由于熔融态的金属锂和硅混合形成的锂硅合金降低了熔融态金属锂表面能，使得熔融态金属锂更容易进入骨架碳材料的内部，因此锂硅合金-骨架碳复合负极比金属锂-骨架碳材料具有更高的比容量。图5显示实施例2中制备的锂硅合金-骨架碳复合材料的扫描电子显微镜(SEM)照片以及EDS元素分析测试结果，其中：A为材料形貌的SEM图；B为复合材料中碳元素分布的EDS测试图；C为复合材料中Si元素分布的EDS测试图，并且以上图中的放大倍数为5000倍。由图5(A)可知，所得到的锂硅合金-骨架碳复合材料基本上保持了作为载体的多孔碳材料载体的球形形状。此外，从图5(B)和(C)的比较可知，金属硅的分布与碳分布基本吻合，说明金属硅均匀地分布在骨架碳的表面和孔隙内。图6显示实施例2中制备的锂硅合金-骨架碳复合材料的恒流充放电测试结果与根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料的恒流充放电测试结果的比较。从该图可以看出，锂硅合金-骨架碳复合材料在开始时极化电压很小，表明材料具有大的比表面积，能极大地降低电流密度，有效抑制锂枝晶的生成。并且由于合金中硅的存在，在材料内部起到促进金属锂沉积的作用，因此该材料比根据WO 2015139660A1中的方法制备的金属锂-骨架碳复合材料具有了更加出色的循环稳定性。According to the method described in the above test method section on the morphology and lithium plating lithium cycle performance, the morphology of the lithium silicon alloy-skeletal carbon composite obtained above and the lithium plating lithium plating cycle performance were tested, and The lithium-plated carbon composite material obtained above was tested for lithium plating cycle performance. 4 shows a discharge curve of a lithium silicon alloy-skeletal carbon composite prepared in Example 2 and a discharge curve of a metallic lithium-skeletal carbon composite prepared according to the method of WO 2015139660 A1. Comparison of lines. The lithium silicon alloy formed by the mixing of molten lithium metal and silicon reduces the surface energy of the molten metal lithium, so that the molten metal lithium is more likely to enter the interior of the skeleton carbon material, so the lithium silicon alloy-skeletal carbon composite negative electrode is more than metallic lithium. The skeleton carbon material has a higher specific capacity. 5 shows a scanning electron microscope (SEM) photograph of the lithium silicon alloy-skeletal carbon composite prepared in Example 2 and EDS elemental analysis test results, wherein: A is an SEM image of the material morphology; B is a carbon element in the composite material. The distributed EDS test chart; C is the EDS test chart of the Si element distribution in the composite, and the magnification in the above figure is 5000 times. As is apparent from Fig. 5(A), the obtained lithium silicon alloy-skeletal carbon composite material substantially maintains the spherical shape of the porous carbon material carrier as a carrier. In addition, from the comparison of FIG. 5(B) and (C), the distribution of the metal silicon substantially coincides with the carbon distribution, indicating that the metal silicon is uniformly distributed in the surface and pores of the skeleton carbon. 6 shows a comparison of the results of the constant current charge and discharge test of the lithium silicon alloy-skeletal carbon composite prepared in Example 2 with the constant current charge and discharge test results of the metal lithium-skeletal carbon composite prepared according to the method of WO 2015139660 A1. It can be seen from the figure that the lithium-silicon alloy-skeletal carbon composite material has a small polarization voltage at the beginning, indicating that the material has a large specific surface area, which can greatly reduce the current density and effectively inhibit the formation of lithium dendrites. And because of the presence of silicon in the alloy, it promotes the deposition of metallic lithium inside the material, so the material has more excellent cycle stability than the metallic lithium-skeletal carbon composite prepared according to the method of WO 2015139660A1.

尽管本发明中已经示出和描述了具体的实施方式，但本领域技术人员将懂得，可以用各种替代的和/或等同的实施方式代替所示和所描述的具体实施方式，而不脱离本发明的范围。本申请意欲包括对本发明中讨论的具体实施方式的任何改进或更改。因此，本发明仅受限于权利要求及其等同物。While the invention has been shown and described with respect to the specific embodiments the embodiments of the embodiments The scope of the invention. This application is intended to cover any modifications or variations of the specific embodiments disclosed herein. Therefore, the invention is limited only by the claims and the equivalents thereof.

本领域技术人员应当理解，在不背离本发明范围的情况下，可以进行多种修改和改变。这样的修改和改变意欲落入如后附权利要求所限定的本发明的范围之内。 A person skilled in the art will appreciate that many modifications and changes can be made without departing from the scope of the invention. Such modifications and variations are intended to fall within the scope of the invention as defined by the appended claims.

Claims

一种锂合金-骨架碳复合材料，所述锂合金-骨架碳复合材料包括多孔碳材料载体以及形成在所述多孔碳材料载体的表面上和孔隙内的锂合金。A lithium alloy-skeletal carbon composite material comprising a porous carbon material support and a lithium alloy formed on a surface of the porous carbon material support and in the pores.
根据权利要求1所述的锂合金-骨架碳复合材料，其中所述锂合金由金属锂和选自镁、硅、硼、碳、氮、氧、氟、铝、磷、硫、氯、钙、锌、镓、锗、砷、硒、溴、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、铱、铂、金、汞、铊、铅、铋和钋中的一种或多种元素形成。The lithium alloy-skeletal carbon composite according to claim 1, wherein the lithium alloy is composed of lithium metal and is selected from the group consisting of magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, One of zinc, gallium, antimony, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium, indium, tin, antimony, bismuth, iodine, antimony, platinum, gold, mercury, antimony, lead, antimony and antimony One or more elements are formed.
根据权利要求2所述的锂合金-骨架碳复合材料，其中当所述锂合金由金属锂与另外一种元素形成时，锂合金中锂的重量百分比为70％～99.9％。The lithium alloy-skeletal carbon composite according to claim 2, wherein when the lithium alloy is formed of metallic lithium and another element, the weight percentage of lithium in the lithium alloy is 70% to 99.9%.
根据权利要求2所述的锂合金-骨架碳复合材料，其中当所述锂合金由金属锂与另外多种元素形成时，在所述锂合金中，基于所述锂合金的总重量，所述另外多种元素的重量百分数为0.1-30重量％。The lithium alloy-skeletal carbon composite according to claim 2, wherein when the lithium alloy is formed of metallic lithium and a plurality of other elements, in the lithium alloy, based on the total weight of the lithium alloy, Further, the weight percentage of the plurality of elements is from 0.1 to 30% by weight.
根据权利要求2所述的锂合金-骨架碳复合材料，其中所述锂合金为锂镁合金、锂硅合金、锂铝合金、锂硼合金以及其他多元衍生物。The lithium alloy-skeletal carbon composite according to claim 2, wherein the lithium alloy is a lithium magnesium alloy, a lithium silicon alloy, a lithium aluminum alloy, a lithium boron alloy, and other multivariate derivatives.
根据权利要求1所述的锂合金-骨架碳复合材料，其中基于所述锂合金-骨架碳复合材料的总重量，所述锂合金-骨架碳复合材料中的金属锂含量为45-95重量％。The lithium alloy-skeletal carbon composite according to claim 1, wherein a lithium metal content in the lithium alloy-skeletal carbon composite is 45 to 95% by weight based on the total weight of the lithium alloy-skeletal carbon composite .
根据权利要求1所述的锂合金-骨架碳复合材料，其中所述锂合金-骨架碳复合材料的比容量为1000-2800mAh/g。The lithium alloy-skeletal carbon composite according to claim 1, wherein the lithium alloy-skeletal carbon composite has a specific capacity of from 1,000 to 2,800 mAh/g.
根据权利要求1所述的锂合金-骨架碳复合材料，其中所述多孔碳材料载体选自下列各项中的一种或多种：碳纳米管微球、碳纤维微球、中间相碳微球、乙炔黑碳微球、科琴黑碳微球、Super-P微球、多孔活性炭微球、石墨微球和石墨烯微球。The lithium alloy-skeletal carbon composite according to claim 1, wherein the porous carbon material carrier is one or more selected from the group consisting of carbon nanotube microspheres, carbon fiber microspheres, and mesocarbon microspheres. , acetylene black carbon microspheres, Ketjen black carbon microspheres, Super-P microspheres, porous activated carbon microspheres, graphite microspheres and graphene microspheres.
根据权利要求1所述的锂合金-骨架碳复合材料，其中所述多孔碳材料载体为碳纳米管微球。The lithium alloy-skeletal carbon composite according to claim 1, wherein the porous carbon material carrier is carbon nanotube microspheres.
根据权利要求9所述的锂合金-骨架碳复合材料，其中所述碳纳米管微球具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。The lithium alloy-skeletal carbon composite according to claim 9, wherein the carbon nanotube microspheres have a microspherical solid aggregate structure, a spherical aggregate structure, a spheroidal aggregate structure, a porous spherical aggregate structure, and a doughnut aggregate structure. Any one.
根据权利要求9所述的锂合金-骨架碳复合材料，其中： The lithium alloy-skeletal carbon composite according to claim 9, wherein:

所述碳纳米管微球的平均直径为1μm至100μm；和/或The carbon nanotube microspheres have an average diameter of from 1 μm to 100 μm; and/or

所述碳纳米管微球的电导率为1×10^-3至10³S·cm^-1；和/或The carbon nanotube microspheres have a conductivity of 1×10 ⁻³ to 10 ³ S·cm ^-1 ; and/or

所述碳纳米管微球的最大可承受压力为20MPa；和/或The maximum compressive pressure of the carbon nanotube microspheres is 20 MPa; and/or

所述碳纳米管微球的比表面积为100至1500m²/g；和/或The carbon nanotube microspheres have a specific surface area of 100 to 1500 m ² /g; and/or

所述碳纳米管微球所含孔隙的孔径为1nm至200nm。The pores of the carbon nanotube microspheres have a pore diameter of from 1 nm to 200 nm.
根据权利要求9所述的锂合金-骨架碳复合材料，其中所述碳纳米管包括多壁碳纳米管、双壁碳纳米管和单壁碳纳米管中的任意一种或两种以上的组合。The lithium alloy-skeletal carbon composite according to claim 9, wherein the carbon nanotubes comprise any one or a combination of two or more of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes. .
一种用于制备锂合金-骨架碳复合材料的方法，所述方法包括在惰性气氛下依次进行下列步骤：A method for preparing a lithium alloy-skeletal carbon composite, the method comprising sequentially performing the following steps under an inert atmosphere:

(1)将金属锂加热到180-220℃的温度，以得到熔融锂；(1) heating lithium metal to a temperature of 180-220 ° C to obtain molten lithium;

(2)在500-800转/秒的转速的搅拌下，将步骤(1)中得到的熔融锂升温至220-1000℃，加入一种或多种元素熔炼得到熔融状态的锂合金，加入的所述元素选自镁、硅、硼、碳、氮、氧、氟、铝、磷、硫、氯、钙、锌、镓、锗、砷、硒、溴、钌、铑、钯、银、镉、铟、锡、锑、碲、碘、铱、铂、金、汞、铊、铅、铋和钋中的一种或多种；(2) heating the molten lithium obtained in the step (1) to 220-1000 ° C under stirring at a rotation speed of 500-800 rpm, adding one or more elements to obtain a molten lithium alloy, and adding The element is selected from the group consisting of magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminum, phosphorus, sulfur, chlorine, calcium, zinc, gallium, antimony, arsenic, selenium, bromine, antimony, bismuth, palladium, silver, cadmium. , one or more of indium, tin, antimony, bismuth, iodine, antimony, platinum, gold, mercury, antimony, lead, antimony and bismuth;

(3)向处于在500-800转/秒的转速的搅拌下的步骤(2)中得到的所述处于熔融状态的锂合金中加入多孔碳材料载体，继续搅拌20-40分钟，以得到所述锂合金-骨架碳复合材料。(3) adding a porous carbon material carrier to the lithium alloy in a molten state obtained in the step (2) at a stirring speed of 500-800 rpm, and stirring is continued for 20-40 minutes to obtain a Lithium alloy-skeletal carbon composite.
根据权利要求13所述用于制备锂合金-骨架碳复合材料的方法，其中当所述锂合金由金属锂与另外一种元素形成时，所述的锂合金中锂的重量百分比为70％至99.9％。A method for producing a lithium alloy-skeletal carbon composite according to claim 13, wherein when said lithium alloy is formed of metallic lithium and another element, said lithium alloy has a weight percentage of lithium of 70% to 99.9%.
根据权利要求13所述用于制备锂合金-骨架碳复合材料的方法，其中当由金属锂与另外多种元素形成所述锂合金时，基于所述锂合金的总重量，所述另外多种元素的投料重量百分数为0.1-30重量％。A method for producing a lithium alloy-skeletal carbon composite according to claim 13, wherein when said lithium alloy is formed of metallic lithium and a plurality of other elements, said additional plurality based on the total weight of said lithium alloy The weight percentage of the charge of the element is from 0.1 to 30% by weight.
根据权利要求13所述用于制备锂合金-骨架碳复合材料的方法，其中所述锂合金为锂镁合金、锂硅合金、锂铝合金、锂硼合金以及其他多元衍生物。The method for producing a lithium alloy-skeletal carbon composite according to claim 13, wherein the lithium alloy is a lithium magnesium alloy, a lithium silicon alloy, a lithium aluminum alloy, a lithium boron alloy, and other multivariate derivatives.
根据权利要求13所述用于制备锂合金-骨架碳复合材料的方法，其中基于所述锂合金-骨架碳复合材料的总重量，所述锂合金-骨架碳复合材料中的金属锂含量为45-95重量％。 The method for producing a lithium alloy-skeletal carbon composite according to claim 13, wherein the lithium metal content in the lithium alloy-skeletal carbon composite is 45 based on the total weight of the lithium alloy-skeletal carbon composite -95% by weight.
根据权利要求13所述用于制备锂合金-骨架碳复合材料的方法，其中所述锂合金-骨架碳复合材料的比容量为1000-2800mAh/g。The method for producing a lithium alloy-skeletal carbon composite according to claim 13, wherein the lithium alloy-skeletal carbon composite has a specific capacity of from 1,000 to 2,800 mAh/g.
根据权利要求13所述用于制备锂合金-骨架碳复合材料的方法，其中所述多孔碳材料载体选自下列各项中的一种或多种：碳纳米管微球、碳纤维微球、中间相碳微球、乙炔黑碳微球、科琴黑碳微球、Super-P微球、多孔活性炭微球、石墨微球和石墨烯微球。The method for producing a lithium alloy-skeletal carbon composite according to claim 13, wherein the porous carbon material carrier is one or more selected from the group consisting of carbon nanotube microspheres, carbon fiber microspheres, and intermediate Phase carbon microspheres, acetylene black carbon microspheres, Ketjen black carbon microspheres, Super-P microspheres, porous activated carbon microspheres, graphite microspheres, and graphene microspheres.
根据权利要求13所述用于制备锂合金-骨架碳复合材料的方法，其中所述多孔碳材料载体为碳纳米管微球。The method for producing a lithium alloy-skeletal carbon composite according to claim 13, wherein the porous carbon material carrier is carbon nanotube microspheres.
根据权利要求20所述用于制备锂合金-骨架碳复合材料的方法，其中所述碳纳米管微球具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。The method for producing a lithium alloy-skeletal carbon composite according to claim 20, wherein said carbon nanotube microspheres have a microspherical solid aggregate structure, a spherical aggregate structure, a spherical aggregate structure, a porous spherical aggregate structure, and a doughnut shape. Any of aggregating structures.
根据权利要求20所述用于制备锂合金-骨架碳复合材料的方法，其中：A method for preparing a lithium alloy-skeletal carbon composite according to claim 20, wherein:

所述碳纳米管微球的平均直径为1μm至100μm；和/或The carbon nanotube microspheres have an average diameter of from 1 μm to 100 μm; and/or

所述碳纳米管微球的电导率为1×10^-3至10³S·cm^-1；和/或The carbon nanotube microspheres have a conductivity of 1×10 ⁻³ to 10 ³ S·cm ^-1 ; and/or

所述碳纳米管微球的最大可承受压力为20MPa；和/或The maximum compressive pressure of the carbon nanotube microspheres is 20 MPa; and/or

所述碳纳米管微球的比表面积为100至1500m²/g；和/或The carbon nanotube microspheres have a specific surface area of 100 to 1500 m ² /g; and/or

所述碳纳米管微球所含孔隙的孔径为1nm至200nm。The pores of the carbon nanotube microspheres have a pore diameter of from 1 nm to 200 nm.
根据权利要求20所述用于制备锂合金-骨架碳复合材料的方法，其中所述碳纳米管包括多壁碳纳米管、双壁碳纳米管和单壁碳纳米管中的任意一种或两种以上的组合。The method for preparing a lithium alloy-skeletal carbon composite according to claim 20, wherein the carbon nanotubes comprise any one or two of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes. More than one combination.
一种用于二次电池的负极，其中所述负极的材料为根据权利要求1至12中任一项所述的锂合金-骨架碳复合材料，或者所述负极的材料由根据权利要求13至23中任一项所述的用于制备锂合金-骨架碳复合材料的方法制备。A negative electrode for a secondary battery, wherein the material of the negative electrode is the lithium alloy-skeletal carbon composite material according to any one of claims 1 to 12, or the material of the negative electrode is according to claim 13 The method for producing a lithium alloy-skeletal carbon composite according to any one of 23, which is prepared.
一种二次电池，所述二次电池包含根据权利要求24所述的用于二次电池的负极。A secondary battery comprising the negative electrode for a secondary battery according to claim 24.
根据权利要求25所述的二次电池，所述的锂电池包括二次电池和一次电池。 The secondary battery according to claim 25, wherein the lithium battery comprises a secondary battery and a primary battery.