CN117747764A - Silicon-carbon composite material, preparation method thereof, negative electrode active material, negative electrode plate, electrochemical device and vehicle - Google Patents

Silicon-carbon composite material, preparation method thereof, negative electrode active material, negative electrode plate, electrochemical device and vehicle Download PDF

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CN117747764A
CN117747764A CN202211150663.2A CN202211150663A CN117747764A CN 117747764 A CN117747764 A CN 117747764A CN 202211150663 A CN202211150663 A CN 202211150663A CN 117747764 A CN117747764 A CN 117747764A
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silicon
carbon
carbon composite
composite material
graphite
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宋怀河
张家鹏
李昂
张鹏
李叶晶
屈国莹
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Beijing University of Chemical Technology
Beijing CHJ Automobile Technology Co Ltd
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Beijing University of Chemical Technology
Beijing CHJ Automobile Technology Co Ltd
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Abstract

The present disclosure relates to the field of electrochemical technology, and more particularly, to a silicon-carbon composite material, a method of preparing the same, a negative electrode active material, a negative electrode tab, an electrochemical device, and a vehicle, the silicon-carbon composite material including a graphite material and a silicon-carbon material fixed in a gap between the graphite materials. In the silicon-carbon composite material, the silicon-carbon material is wrapped by the graphite material, so that the volume expansion of silicon in the lithiation process can be effectively inhibited, and the battery has stable cycle performance when the silicon-carbon composite material is used as a negative electrode material of a lithium ion battery.

Description

硅碳复合材料及其制备方法、负极活性材料、负极极片、电化 学装置和车辆Silicon-carbon composite materials and preparation methods thereof, negative active materials, negative electrode sheets, electrochemical equipment and vehicles

技术领域Technical field

本公开涉及电化学技术领域,尤其涉及一种硅碳复合材料及其制备方法、负极活性材料、负极极片、电化学装置和车辆。The present disclosure relates to the field of electrochemistry technology, and in particular to a silicon-carbon composite material and a preparation method thereof, anode active material, anode plate, electrochemical device and vehicle.

背景技术Background technique

随着电子设备、电动汽车的高速发展,各类电子设备对二次电池的快充性能提出越来越高的要求。例如,锂离子电池的快充和续航已然成为衡量电池的重要指标。目前商业化锂离子电池的负极多为石墨材料。然而,随着科技高速发展,石墨材料已经不能满足人们的发展需求(理论容量372mAh/g)。并且石墨材料在充放电过程中,锂离子只能通过石墨的端面进行嵌入和脱出,扩散路径长,严重影响锂离子扩散速度,不能满足快充电池的需求。With the rapid development of electronic equipment and electric vehicles, various types of electronic equipment have put forward increasingly higher requirements for the fast charging performance of secondary batteries. For example, the fast charging and battery life of lithium-ion batteries have become important indicators for measuring batteries. At present, most of the negative electrodes of commercial lithium-ion batteries are graphite materials. However, with the rapid development of science and technology, graphite materials can no longer meet people's development needs (theoretical capacity 372mAh/g). Moreover, during the charging and discharging process of graphite materials, lithium ions can only be embedded and extracted through the end faces of graphite. The diffusion path is long, which seriously affects the lithium ion diffusion speed and cannot meet the needs of fast-charging batteries.

为了提高快充性能,相关技术中,针对负极活性材料的结构和/或组成进行了改进,例如采用含硅材料,但硅在锂化过程中会发生体积膨胀,从而影响锂离子电池的循环性能。In order to improve fast charging performance, in related technologies, the structure and/or composition of the negative active material has been improved, such as using silicon-containing materials. However, silicon will expand in volume during the lithiation process, thus affecting the cycle performance of lithium-ion batteries. .

发明内容Contents of the invention

为了解决上述技术问题,本公开提供了一种硅碳复合材料及其制备方法、负极活性材料、负极极片、电化学装置和车辆,本公开的硅碳复合材料具有更好的循环性能。In order to solve the above technical problems, the present disclosure provides a silicon-carbon composite material and a preparation method thereof, a negative active material, a negative electrode sheet, an electrochemical device and a vehicle. The silicon-carbon composite material of the present disclosure has better cycle performance.

本公开提供了一种硅碳复合材料,包括石墨材料以及固定于石墨材料间的空隙中的硅碳材料。The present disclosure provides a silicon-carbon composite material, including graphite material and silicon-carbon material fixed in the gaps between the graphite materials.

可选的,硅碳材料为核壳结构,硅碳材料的内核为纳米硅,硅碳材料的外壳为碳层;和/或,硅碳材料为硅碳母粒,硅碳母粒的粒径为1μm~5μm。Optionally, the silicon carbon material has a core-shell structure, the core of the silicon carbon material is nano-silicon, and the outer shell of the silicon carbon material is a carbon layer; and/or the silicon carbon material is a silicon carbon masterbatch, and the particle size of the silicon carbon masterbatch is It is 1μm~5μm.

可选的,石墨材料和硅碳材料两者形成硅碳复合颗粒,硅碳复合颗粒的粒径为10μm~80μm。Optionally, the graphite material and the silicon-carbon material form silicon-carbon composite particles, and the particle size of the silicon-carbon composite particles is 10 μm to 80 μm.

可选的,硅碳材料中硅元素的质量百分比含量为20%~60%;和/或,硅碳复合材料中硅碳材料的质量百分比含量为20%~50%;硅碳复合材料中石墨材料的质量百分比含量为48%~79%。Optionally, the mass percentage content of the silicon element in the silicon carbon material is 20% to 60%; and/or the mass percentage content of the silicon carbon material in the silicon carbon composite material is 20% to 50%; the graphite in the silicon carbon composite material The mass percentage content of the material is 48% to 79%.

可选的,硅碳复合材料中还包括导电剂,导电剂穿插于硅碳材料和石墨材料之间,用于在硅碳复合材料内部形成导电网络,优选地,硅碳复合材料中导电剂的质量百分比含量为1%~2%;硅碳复合材料中还包括粘结剂,硅碳材料与石墨材料之间、石墨材料之间通过粘合剂连接,硅碳复合颗粒之间通过粘合剂连接,优选地,粘合剂占硅碳复合材料总重量的2%~20%。Optionally, the silicon carbon composite material also includes a conductive agent. The conductive agent is interspersed between the silicon carbon material and the graphite material to form a conductive network inside the silicon carbon composite material. Preferably, the conductive agent in the silicon carbon composite material is The mass percentage content is 1% to 2%; the silicon-carbon composite material also includes a binder. The silicon-carbon material and the graphite material and the graphite materials are connected through an adhesive, and the silicon-carbon composite particles are connected through an adhesive. For connection, preferably, the adhesive accounts for 2% to 20% of the total weight of the silicon-carbon composite material.

可选的,导电剂选自碳纳米材料,优选地,碳纳米材料选自零维、一维、二维和三维碳纳米材料中的至少一种;石墨材料包括石墨和类石墨材料中的至少一种,石墨选自人造石墨和天然石墨中的至少一种;类石墨材料选自洋葱状碳微球和MCMB中的至少一种;优选地,石墨材料的粒径为1μm~25μm。Optionally, the conductive agent is selected from carbon nanomaterials. Preferably, the carbon nanomaterials are selected from at least one of zero-dimensional, one-dimensional, two-dimensional and three-dimensional carbon nanomaterials; graphite materials include at least one of graphite and graphite-like materials. One, the graphite is selected from at least one of artificial graphite and natural graphite; the graphite-like material is selected from at least one of onion-shaped carbon microspheres and MCMB; preferably, the particle size of the graphite material is 1 μm to 25 μm.

可选的,硅碳复合材料的振实密度为0.4~0.6g/cm3,硅碳复合材料的储锂容量为400~2000mAh/g。Optionally, the tap density of the silicon-carbon composite material is 0.4~0.6g/cm 3 , and the lithium storage capacity of the silicon-carbon composite material is 400~2000mAh/g.

本公开还提供了上述硅碳复合材料的制备方法,至少包括以下步骤:The present disclosure also provides a method for preparing the above-mentioned silicon-carbon composite material, which at least includes the following steps:

S1、制备硅碳材料;S1. Preparation of silicon carbon materials;

S2、取硅碳材料、石墨材料和导电剂,混合均匀,加入粘结剂前体溶液后继续混合;S2. Take the silicon carbon material, graphite material and conductive agent, mix them evenly, add the binder precursor solution and continue mixing;

S3、将混合后的原料在惰性气氛条件下碳化,得到硅碳复合材料。S3. Carbonize the mixed raw materials under inert atmosphere conditions to obtain silicon-carbon composite materials.

可选的,在S1中,将纳米硅分散于液态碳源中,获得分散液,将分散液在惰性气氛下热解并保温,即得硅碳材料,优选地,液态碳源选自链状烃、环状烃或混合烃;和/或,Optionally, in S1, nano-silicon is dispersed in a liquid carbon source to obtain a dispersion. The dispersion is pyrolyzed and kept warm under an inert atmosphere to obtain a silicon carbon material. Preferably, the liquid carbon source is selected from chain materials. Hydrocarbons, cyclic hydrocarbons or mixed hydrocarbons; and/or,

在S2中,取硅碳材料、石墨材料和导电剂先在湿法造粒机中混合5~10分钟,切割转速为1500~2500rpm,混合转速为120~180rpm;然后加入粘结剂前体溶液再搅拌10~30分钟,切割转速为1500~2500rpm,混合转速为120~180rpm;和/或,In S2, take the silicon carbon material, graphite material and conductive agent and mix them in a wet granulator for 5 to 10 minutes, with a cutting speed of 1500 to 2500 rpm and a mixing speed of 120 to 180 rpm; then add the binder precursor solution Stir for another 10 to 30 minutes, with a cutting speed of 1500 to 2500 rpm and a mixing speed of 120 to 180 rpm; and/or,

在S3中,碳化的温度为600℃~1200℃,碳化的时间为1~3小时。In S3, the carbonization temperature is 600°C to 1200°C, and the carbonization time is 1 to 3 hours.

可选的,在S2中,粘结剂前体溶液中溶质的质量百分比浓度为2%~30%,粘结剂前体溶液的添加量为硅碳材料、石墨材料和导电剂总质量的20%~120%;Optionally, in S2, the mass percentage concentration of the solute in the binder precursor solution is 2% to 30%, and the added amount of the binder precursor solution is 20% of the total mass of the silicon carbon material, graphite material and conductive agent. %~120%;

优选的,粘结剂前体溶液选自水性粘结剂或油性粘结剂;优选地,水性粘结剂选自羧甲基纤维素钠水溶液、海藻酸钠水溶液、聚丙烯酸水溶液中的至少一种;优选地,油性粘结剂选自聚偏氟乙烯/N,N-二甲基甲酰胺溶液、沥青-吡啶混合物、沥青-四氢呋喃混合物中的至少一种。Preferably, the binder precursor solution is selected from aqueous binders or oily binders; preferably, the aqueous binder is selected from at least one of sodium carboxymethylcellulose aqueous solution, sodium alginate aqueous solution, and polyacrylic acid aqueous solution. kind; Preferably, the oily binder is selected from at least one of polyvinylidene fluoride/N,N-dimethylformamide solution, asphalt-pyridine mixture, and asphalt-tetrahydrofuran mixture.

本公开还提供了一种负极活性材料,包括上述硅碳复合材料或如上述制备方法制得的硅碳复合材料。The present disclosure also provides a negative active material, including the above-mentioned silicon-carbon composite material or the silicon-carbon composite material prepared by the above-mentioned preparation method.

本公开还提供了一种负极极片,负极极片中的负极活性材料选自上述负极活性材料。The present disclosure also provides a negative electrode piece, and the negative active material in the negative electrode piece is selected from the above-mentioned negative active materials.

本公开还提供了一种电化学装置,包括正极极片、负极极片和隔离膜,负极极片为上述负极极片。The present disclosure also provides an electrochemical device, including a positive electrode piece, a negative electrode piece and an isolation film. The negative electrode piece is the above-mentioned negative electrode piece.

本公开还提供了一种车辆,车辆中包含上述电化学装置。The present disclosure also provides a vehicle, which includes the above-mentioned electrochemical device.

本公开实施例提供的技术方案与现有技术相比具有如下优点:Compared with the existing technology, the technical solution provided by the embodiments of the present disclosure has the following advantages:

在本公开的硅碳复合材料中,硅碳材料固定在石墨材料间的空隙中,也即硅碳材料被石墨材料包裹,从而可有效抑制硅碳材料中的硅在锂化过程中的体积膨胀,其作为锂离子电池的负极材料使用时,能保证电池具有稳定的循环性能。In the silicon-carbon composite material of the present disclosure, the silicon-carbon material is fixed in the gaps between the graphite materials, that is, the silicon-carbon material is wrapped by the graphite material, which can effectively suppress the volume expansion of silicon in the silicon-carbon material during the lithiation process. , when used as anode material for lithium-ion batteries, it can ensure stable cycle performance of the battery.

附图说明Description of drawings

此处的附图被并入说明书中并构成本说明书的一部分,示出了符合本公开的实施例,并与说明书一起用于解释本发明的原理。The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description serve to explain the principles of the invention.

为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,对于本领域普通技术人员而言,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those of ordinary skill in the art, It is said that other drawings can be obtained based on these drawings without exerting creative labor.

图1为本公开实施例的硅碳复合颗粒的结构示意图;Figure 1 is a schematic structural diagram of silicon-carbon composite particles according to an embodiment of the present disclosure;

图2和图3为本公开实施例的硅碳复合材料的电子扫描显微镜照片;Figures 2 and 3 are scanning electron microscope photographs of silicon-carbon composite materials according to embodiments of the present disclosure;

图4为本公开实施例的半电池的充放电性能测试结果;Figure 4 shows the charge and discharge performance test results of the half-cell according to the embodiment of the present disclosure;

图5为本公开实施例的全电池的倍率性能测试结果。Figure 5 shows the rate performance test results of the full battery according to the embodiment of the present disclosure.

其中:in:

1-石墨材料;1- Graphite material;

2-粘结剂;2-Binder;

3-硅碳材料。3-Silicon carbon material.

具体实施方式Detailed ways

为了能够更清楚地理解本公开的上述目的、特征和优点,下面将对本发明的方案进行进一步描述。需要说明的是,在不冲突的情况下,本公开的实施例及实施例中的特征可以相互组合。In order to understand the above objects, features and advantages of the present disclosure more clearly, the solution of the present invention will be further described below. It should be noted that, as long as there is no conflict, the embodiments of the present disclosure and the features in the embodiments can be combined with each other.

在下面的描述中阐述了很多具体细节以便于充分理解本公开,但本公开还可以采用其他不同于在此描述的方式来实施;显然,说明书中的实施例只是本公开的一部分实施例,而不是全部的实施例。Many specific details are set forth in the following description to fully understand the present disclosure, but the present disclosure can also be implemented in other ways different from those described here; obviously, the embodiments in the description are only part of the embodiments of the present disclosure, and Not all examples.

为了进一步提高现有负极活性材料的循环性能,本公开实施例的第一方面提出一种硅碳复合材料,包括石墨材料以及固定于石墨材料间的空隙中的硅碳材料;硅碳复合颗粒的结构示意图如图1所示。由图1可知,石墨材料1的颗粒堆积后在颗粒之间形成有空隙,硅碳材料3被固定并限域在石墨材料1的颗粒紧密堆积形成的空隙中,有效抑制硅在锂化过程中的体积膨胀,使其作为锂离子电池的负极材料使用时,使电池具有稳定的循环性能。In order to further improve the cycle performance of existing negative active materials, the first aspect of the embodiment of the present disclosure proposes a silicon-carbon composite material, including a graphite material and a silicon-carbon material fixed in the gaps between the graphite materials; the silicon-carbon composite particles The structural diagram is shown in Figure 1. As can be seen from Figure 1, after the particles of graphite material 1 are accumulated, gaps are formed between the particles. The silicon carbon material 3 is fixed and confined in the gaps formed by the close accumulation of particles of graphite material 1, effectively inhibiting the formation of silicon during the lithiation process. The volume expansion enables the battery to have stable cycle performance when used as anode material for lithium-ion batteries.

作为本公开实施例的一种改进,硅碳复合材料中的硅碳材料为核壳结构,内核为纳米硅,也即纳米硅粉,外壳为碳层。As an improvement of the embodiment of the present disclosure, the silicon carbon material in the silicon carbon composite material has a core-shell structure, the core is nano silicon, that is, nano silicon powder, and the outer shell is a carbon layer.

作为本公开实施例的一种改进,石墨材料和硅碳材料两者形成硅碳复合颗粒,硅碳复合颗粒的粒径为10μm~80μm,硅碳复合颗粒的粒径范围的最小值可为10μm、13μm、15μm、18μm、20μm、22μm、25μm,硅碳复合颗粒的粒径范围的最大值可为80μm、75μm、70μm、65μm、60μm、55μm、50μm、45μm、40μm、35μm,并优选为10μm~40μm。作为本公开实施例的一种改进,硅碳材料中硅元素的质量百分比含量为20%~60%,例如可为20%、30%、40%、50%、60%,优选50%~60%,硅元素的占比增高可以更有效提升电池容量。As an improvement of the embodiment of the present disclosure, the graphite material and the silicon carbon material form silicon carbon composite particles. The particle size of the silicon carbon composite particles is 10 μm ~ 80 μm. The minimum value of the particle size range of the silicon carbon composite particles can be 10 μm. , 13 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, the maximum value of the particle size range of the silicon carbon composite particles can be 80 μm, 75 μm, 70 μm, 65 μm, 60 μm, 55 μm, 50 μm, 45 μm, 40 μm, 35 μm, and is preferably 10 μm. ~40μm. As an improvement of the embodiment of the present disclosure, the mass percentage content of silicon element in the silicon carbon material is 20% to 60%, for example, it can be 20%, 30%, 40%, 50%, 60%, preferably 50% to 60% %, the increased proportion of silicon element can more effectively increase the battery capacity.

作为本公开实施例的一种改进,硅碳材料为硅碳母粒,硅碳母粒的粒径为1μm~5μm,硅碳母粒较小而均匀的颗粒可以进一步提高负极材料的振实密度,提高电池的能量密度。As an improvement of the embodiment of the present disclosure, the silicon carbon material is silicon carbon masterbatch, and the particle size of the silicon carbon masterbatch is 1 μm to 5 μm. The smaller and uniform particles of the silicon carbon masterbatch can further increase the tap density of the negative electrode material. , improve the energy density of the battery.

作为本公开实施例的一种改进,石墨材料包括石墨和类石墨材料中的至少一种,石墨选自人造石墨和天然石墨中的至少一种;类石墨材料选自洋葱状碳微球和中间相炭微球(Mesocarbon microbeads,简称MCMB)中的至少一种。洋葱状碳微球指石墨化洋葱碳,内核为富勒烯,石墨层为球状,整体呈现洋葱形状,其粒径为1μm~25μm,根据其型号不同,粒径范围的最小值可以为2μm、3μm、4μm、5μm、7μm、9μm;粒径范围的最小值12μm、15μm、18μm、20μm、22μm、25μm,优选为5μm~25μm或3μm~15μm。为了便于在硅碳复合颗粒中形成用于固定硅碳材料的空隙,石墨材料优选球形或者接近球形的原料。并进一步优选洋葱状碳微球,因其形状为球型,堆积时可以实现更高的密度,且石墨层呈洋葱状排列,所以在受到大的应力时不会发生解离。As an improvement of the embodiment of the present disclosure, the graphite material includes at least one of graphite and graphite-like materials, the graphite is selected from at least one of artificial graphite and natural graphite; the graphite-like material is selected from onion-like carbon microspheres and intermediate At least one of Mesocarbon microbeads (MCMB for short). Onion-like carbon microspheres refer to graphitized onion carbon. The core is fullerene. The graphite layer is spherical. The overall shape is onion. Its particle size is 1μm~25μm. Depending on its model, the minimum particle size range can be 2μm, 3 μm, 4 μm, 5 μm, 7 μm, 9 μm; the minimum value of the particle size range is 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, preferably 5 μm to 25 μm or 3 μm to 15 μm. In order to facilitate the formation of voids for fixing the silicon-carbon material in the silicon-carbon composite particles, the graphite material is preferably a spherical or nearly spherical raw material. Onion-shaped carbon microspheres are further preferred because they are spherical in shape and can achieve higher density when stacked. The graphite layers are arranged in an onion shape, so they will not dissociate when subjected to large stress.

作为本公开实施例的一种改进,硅碳复合材料中硅碳母粒的质量百分比含量为20%~50%,例如可为25%、30%、40%、45%,优选为25%~40%;硅碳复合材料中石墨材料的质量百分比含量为48%~79%,例如可为50%、55%、60%、65%、70%、75%,优选为48%~74%。在特定质量比以及材料粒径分布的共同作用下,从而可进一步将硅碳材料全部固定于石墨材料之间所形成的空隙中,同时保证硅碳复合材料中含有足够量的硅碳材料保证电池容量。As an improvement of the embodiment of the present disclosure, the mass percentage content of silicon carbon masterbatch in the silicon carbon composite material is 20% to 50%, for example, it can be 25%, 30%, 40%, 45%, preferably 25% to 45%. 40%; the mass percentage content of graphite material in the silicon-carbon composite material is 48% to 79%, for example, it can be 50%, 55%, 60%, 65%, 70%, 75%, preferably 48% to 74%. Under the combined action of a specific mass ratio and material particle size distribution, all silicon-carbon materials can be further fixed in the gaps formed between graphite materials, while ensuring that the silicon-carbon composite material contains a sufficient amount of silicon-carbon material to ensure the battery capacity.

作为本公开实施例的一种改进,硅碳复合材料中还包括导电剂,导电剂穿插于硅碳材料和石墨材料之间,用于在硅碳复合颗粒内部形成导电网络,形成导电网络可以有效实现电子的高速转移以及锂离子的快速传递,使用该材料其作为锂离子电池的负极材料使用时,电池具有更好的快充性能。As an improvement to the embodiment of the present disclosure, the silicon-carbon composite material also includes a conductive agent. The conductive agent is interspersed between the silicon-carbon material and the graphite material to form a conductive network inside the silicon-carbon composite particles. The conductive network can be effectively formed. Achieve high-speed transfer of electrons and rapid transfer of lithium ions. When using this material as an anode material for lithium-ion batteries, the battery has better fast charging performance.

作为本公开实施例的一种改进,导电剂选自碳纳米材料,碳纳米材料选自零维、一维、二维和三维碳纳米材料中的至少一种。碳纳米材料是指在至少一个维度(如长、宽、高)上的尺寸在1nm~100nm之间的材料。零维碳纳米材料是指每一个维度的尺寸都在1nm~100nm之间碳纳米材料,如富勒烯C60和C70。一维纳米材料是三个维度中有两个维度的尺寸不在1nm~100nm之间的材料,如碳纳米管;二维纳米材料是指三个维度中有一个维度的尺寸不在1nm~100nm之间的材料,如石墨烯;三维纳米材料是指由零维、一维、二维中的一种或多种基本结构单元组成的复合材料,例如炭黑。As an improvement of the embodiment of the present disclosure, the conductive agent is selected from carbon nanomaterials, and the carbon nanomaterials are selected from at least one of zero-dimensional, one-dimensional, two-dimensional and three-dimensional carbon nanomaterials. Carbon nanomaterials refer to materials with dimensions ranging from 1 nm to 100 nm in at least one dimension (such as length, width, and height). Zero-dimensional carbon nanomaterials refer to carbon nanomaterials with the size of each dimension between 1nm and 100nm, such as fullerene C60 and C70. One-dimensional nanomaterials are materials in which two of the three dimensions are not between 1nm and 100nm, such as carbon nanotubes; two-dimensional nanomaterials are materials in which one of the three dimensions is not between 1nm and 100nm. materials, such as graphene; three-dimensional nanomaterials refer to composite materials composed of one or more basic structural units in zero, one, and two dimensions, such as carbon black.

作为本公开实施例的一种改进,碳纳米材料选自石墨烯。石墨烯为二维结构,不仅导电性好,可以连接硅碳材料和石墨材料,并对硅碳颗粒进行包覆。As an improvement of the embodiment of the present disclosure, the carbon nanomaterial is selected from graphene. Graphene has a two-dimensional structure, which not only has good electrical conductivity, but can also connect silicon-carbon materials and graphite materials and coat silicon-carbon particles.

作为本公开实施例的一种改进,硅碳复合材料中导电剂的质量比为1%~2%,例如可为1%、1.2%、1.5%、1.8%、2%。该比例内的导电剂可有效在硅碳复合颗粒内部形成导电网络。As an improvement of the embodiment of the present disclosure, the mass ratio of the conductive agent in the silicon-carbon composite material is 1% to 2%, for example, it can be 1%, 1.2%, 1.5%, 1.8%, or 2%. The conductive agent within this proportion can effectively form a conductive network inside the silicon-carbon composite particles.

作为本公开实施例的一种改进,硅碳复合材料中还包括粘结剂,示意图如图1所示,硅碳材料3与石墨材料1之间、石墨材料1之间通过粘合剂2连接。并且,在硅碳复合颗粒之间也可以通过粘合剂进一步连接。粘结剂为经高温碳化而成热解碳,从而将各原料颗粒稳定的固定在一起。As an improvement of the embodiment of the present disclosure, the silicon-carbon composite material also includes a binder. The schematic diagram is shown in Figure 1. The silicon-carbon material 3 and the graphite material 1 and the graphite materials 1 are connected through the binder 2. . Furthermore, the silicon-carbon composite particles may be further connected through an adhesive. The binder is pyrolytic carbon that is carbonized at high temperatures, thereby stably fixing the raw material particles together.

作为本公开实施例的一种改进,粘合剂占硅碳复合材料总重量的2%~20%,例如可为3%、5%、8%、10%、15%、18%;并优选为3%~18%,进一步优选为5%~15%。粘合剂的作用为连接、固定各颗粒,因此在硅碳复合材料中的质量占比较小。而如果粘合剂的占比过大,则会影响硅碳复合材料振实密度,进而影响其能量密度。As an improvement to the embodiment of the present disclosure, the binder accounts for 2% to 20% of the total weight of the silicon-carbon composite material, for example, it can be 3%, 5%, 8%, 10%, 15%, 18%; and preferably It is 3% to 18%, and more preferably 5% to 15%. The function of the adhesive is to connect and fix the particles, so it accounts for a relatively small mass in the silicon-carbon composite material. If the proportion of binder is too large, it will affect the tap density of silicon-carbon composite materials, thereby affecting its energy density.

作为本公开实施例的一种改进,硅碳复合材料的振实密度为0.4~1g/cm3,例如可为0.5g/cm3、0.6g/cm3、0.7g/cm3、0.75g/cm3、0.9g/cm3、0.95g/cm3。本公开实施例的硅碳复合材料的振实密度高,说明该硅碳复合材料具有更高的能量密度。As an improvement of the embodiment of the present disclosure, the tap density of the silicon-carbon composite material is 0.4-1g/cm3, for example, it can be 0.5g/ cm3 , 0.6g/ cm3 , 0.7g/ cm3 , 0.75g/cm 3 , 0.9g/cm 3 , 0.95g/cm 3 . The tap density of the silicon-carbon composite material in the embodiment of the present disclosure is high, indicating that the silicon-carbon composite material has a higher energy density.

作为本公开实施例的一种改进,硅碳复合材料的储锂容量为400~2000mAh/g,例如可为450mAh/g、500mAh/g、530mAh/g、600mAh/g、700mAh/g、800mAh/g、900mAh/g、1000mAh/g、1200mAh/g。本公开实施例的硅碳复合材料显著高于石墨材料的储锂容量。As an improvement of the embodiment of the present disclosure, the lithium storage capacity of the silicon-carbon composite material is 400-2000mAh/g, for example, it can be 450mAh/g, 500mAh/g, 530mAh/g, 600mAh/g, 700mAh/g, 800mAh/ g, 900mAh/g, 1000mAh/g, 1200mAh/g. The silicon-carbon composite material of the embodiment of the present disclosure has a lithium storage capacity significantly higher than that of graphite material.

本公开实施例的第二方面进一步提出了该硅碳复合材料的制备方法,至少包括以下步骤:The second aspect of the embodiment of the present disclosure further proposes a preparation method of the silicon-carbon composite material, which at least includes the following steps:

S1、制备硅碳材料;S1. Preparation of silicon carbon materials;

S2、取硅碳材料、石墨材料和碳纳米材料,混合均匀,加入粘结剂前体溶液后继续混合;S2. Take the silicon carbon material, graphite material and carbon nanomaterial, mix them evenly, add the binder precursor solution and continue mixing;

S3、将混合后的原料在惰性气氛条件下碳化,得到硅碳复合材料。S3. Carbonize the mixed raw materials under inert atmosphere conditions to obtain silicon-carbon composite materials.

本公开实施例制备方法具有简单、可控的优势,从而可以促进负极活性材料的广泛使用。The preparation method of the embodiment of the present disclosure has the advantages of simplicity and controllability, thereby promoting the widespread use of negative active materials.

在S1中,核壳结构的硅碳材料可采用常规方法制备,并可选择以下方法进行制备:将纳米硅粉分散于液态碳源中,获得分散液,将分散液加入到预热的化学气相热解反应炉中,在惰性气氛下热解并保温,即得硅碳材料。In S1, core-shell structured silicon carbon materials can be prepared by conventional methods, and the following methods can be selected for preparation: disperse nano-silica powder in a liquid carbon source to obtain a dispersion, and add the dispersion to the preheated chemical vapor phase In the pyrolysis reaction furnace, the silicon carbon material is obtained by pyrolysis and heat preservation under an inert atmosphere.

具体的,液态碳源选自链状烃、环状烃或混合烃,如正庚烷、甲苯,也可以选择烃的混合物如工业洗油等。纳米硅粉与液态碳源的质量比可以为1:5~10。预热和热解的温度可采用600℃~1200℃,例如可为700℃、800℃、850℃、900℃、950℃,保温的时间可采用0.5~2小时,例如可为0.5小时、1小时、1.5小时。为了加快分散效率,可采用超声分散的方式,超声的波长和功率可采用常规条件。Specifically, the liquid carbon source is selected from chain hydrocarbons, cyclic hydrocarbons or mixed hydrocarbons, such as n-heptane and toluene, and a mixture of hydrocarbons such as industrial washing oil can also be selected. The mass ratio of nano-silica powder to liquid carbon source can be 1:5-10. The temperature of preheating and pyrolysis can be 600℃~1200℃, for example, it can be 700℃, 800℃, 850℃, 900℃, 950℃. The heat preservation time can be 0.5~2 hours, for example, it can be 0.5 hour, 1 hours, 1.5 hours. In order to speed up the dispersion efficiency, ultrasonic dispersion can be used, and the wavelength and power of ultrasonic can be used under conventional conditions.

作为本公开实施例的一种改进,在S2中,粘结剂前体溶液中溶质的质量百分比浓度为2%~30%,进一步可为3%、5%、10%、15%、20%、25%。As an improvement of the embodiment of the present disclosure, in S2, the mass percentage concentration of the solute in the binder precursor solution is 2% to 30%, and can further be 3%, 5%, 10%, 15%, 20% ,25%.

作为本公开实施例的一种改进,在S2中,粘结剂前体溶液的添加量为硅碳材料、石墨材料和导电剂总质量的20%~120%。粘结剂前体溶液的添加量为进一步可选用硅碳材料、石墨材料和导电剂总质量的30%、40%、50%、60%、70%、80%、90%、100%。As an improvement of the embodiment of the present disclosure, in S2, the amount of the binder precursor solution added is 20% to 120% of the total mass of the silicon carbon material, graphite material and conductive agent. The amount of the binder precursor solution added is 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% of the total mass of the silicon carbon material, graphite material and conductive agent.

作为本公开实施例的一种改进,在S2中,粘结剂前体溶液选自水性粘结剂或油性粘结剂;水性粘结剂是指高分子分子链完全伸展开分散在水中,具体可选自水性PVDF、聚丙烯酸、聚氨酯、聚乙烯醇、聚丙烯酸酯、聚丙烯酸-聚丙烯腈共聚物、聚丙烯酸酯-聚丙烯腈共聚物中的至少一种,也可选自多糖类物质,例如羧甲基纤维素钠、海藻酸钠等。水性粘结剂中溶质的质量百分比浓度可以为10%~20%;例如可为10%、12%、15%、18%。油性粘结剂是指是指高分子分子链完全伸展开分散在油性溶剂中。例如聚偏氟乙烯的油性溶剂溶液、沥青与油性溶剂的混合物等。油性溶剂可选择N,N-二甲基甲酰胺、吡啶、四氢呋喃等粘度较小的有机溶剂。具体的,可选用聚偏氟乙烯/N,N-二甲基甲酰胺溶液、沥青-吡啶混合物、沥青-四氢呋喃混合物。其中,聚偏氟乙烯在N,N-二甲基甲酰胺中的质量百分比浓度可以为10%~20%,例如可为10%、12%、15%、18%;沥青-吡啶混合物中沥青的质量百分比浓度可以为10%~20%,例如可为10%、12%、15%、18%;沥青-四氢呋喃混合物中中沥青的质量百分比浓度可以为10%~20%,例如可为10%、12%、15%、18%。As an improvement of the embodiment of the present disclosure, in S2, the binder precursor solution is selected from a water-based binder or an oil-based binder; a water-based binder refers to a polymer chain that is fully extended and dispersed in water, specifically It can be selected from at least one of water-based PVDF, polyacrylic acid, polyurethane, polyvinyl alcohol, polyacrylate, polyacrylic acid-polyacrylonitrile copolymer, polyacrylate-polyacrylonitrile copolymer, or polysaccharides. Substances such as sodium carboxymethyl cellulose, sodium alginate, etc. The mass percentage concentration of the solute in the water-based binder can be 10% to 20%; for example, it can be 10%, 12%, 15%, or 18%. Oily binder means that the polymer molecular chain is completely extended and dispersed in the oily solvent. For example, the oily solvent solution of polyvinylidene fluoride, the mixture of asphalt and oily solvent, etc. For oily solvents, organic solvents with smaller viscosity such as N,N-dimethylformamide, pyridine, and tetrahydrofuran can be selected. Specifically, polyvinylidene fluoride/N,N-dimethylformamide solution, asphalt-pyridine mixture, and asphalt-tetrahydrofuran mixture can be used. Wherein, the mass percentage concentration of polyvinylidene fluoride in N,N-dimethylformamide can be 10% to 20%, for example, it can be 10%, 12%, 15%, 18%; the asphalt in the asphalt-pyridine mixture The mass percentage concentration of asphalt can be 10% to 20%, for example, it can be 10%, 12%, 15%, 18%; the mass percentage concentration of asphalt in the asphalt-tetrahydrofuran mixture can be 10% to 20%, for example, it can be 10 %, 12%, 15%, 18%.

作为本公开实施例的一种改进,在S2中,取硅碳材料、石墨材料和导电剂先在湿法造粒机中混合5~10分钟,切割转速为1500~2500rpm;混合转速为120~180rpm;然后加入粘结剂前体溶液再搅拌10~30分钟,切割转速为1500~2500rpm,混合转速为120~180rpm。进一步可选择的,湿法造粒机所采用的工作条件为:切割转速可以选用1800rpm、2000rpm、2200rpm,混合转速可以选用125rpm、130rpm、140rpm、150rpm、160rpm、175rpm;并进一步可选用:切割转速为2000rpm,混合转速为150rpm。本公开实施例的步骤2在湿法造粒机中进行,即利用湿法造粒机内部的混合桨对原料进行充分的混合,可以进一步缩短混合的时间,提高生产效率。经造粒后,小颗粒的硅碳材料被限域在石墨颗粒紧密堆积的空隙中,有效抑制硅在锂化过程中的体积膨胀,使硅碳复合材料电极拥有稳定的循环性能。可选用湿法造粒机的型号为:HLSG系列湿法混合机制粒机、GHL系列湿法混合机制粒机、SMG系列湿法混合机制粒机、Diosna混合湿法造粒机。As an improvement of the embodiment of the present disclosure, in S2, the silicon carbon material, graphite material and conductive agent are first mixed in a wet granulator for 5 to 10 minutes, the cutting speed is 1500 to 2500 rpm; the mixing speed is 120 to 120 rpm. 180rpm; then add the binder precursor solution and stir for 10 to 30 minutes, the cutting speed is 1500~2500rpm, and the mixing speed is 120~180rpm. Further optionally, the working conditions used by the wet granulator are: the cutting speed can be selected from 1800rpm, 2000rpm, and 2200rpm, and the mixing speed can be selected from 125rpm, 130rpm, 140rpm, 150rpm, 160rpm, and 175rpm; and further optional: cutting speed is 2000rpm, and the mixing speed is 150rpm. Step 2 of the embodiment of the present disclosure is performed in a wet granulator, that is, the mixing paddle inside the wet granulator is used to fully mix the raw materials, which can further shorten the mixing time and improve production efficiency. After granulation, small particles of silicon-carbon material are confined in the gaps where graphite particles are closely packed, effectively suppressing the volume expansion of silicon during the lithiation process, so that silicon-carbon composite electrodes have stable cycle performance. The models of wet granulators that can be used are: HLSG series wet mixer granulator, GHL series wet mixer granulator, SMG series wet mixer granulator, and Diosna mixed wet granulator.

作为本公开实施例的一种改进,在S3中,碳化的温度可以采用600℃~1200℃,例如可为800℃、900℃、1000℃、1100℃,碳化的时间可采用1~3小时,例如1.5小时、2小时、2.5小时。碳化的目的是为了将粘结剂前体碳化形成粘结剂。As an improvement of the embodiment of the present disclosure, in S3, the carbonization temperature can be 600°C to 1200°C, for example, 800°C, 900°C, 1000°C, 1100°C, and the carbonization time can be 1 to 3 hours. For example, 1.5 hours, 2 hours, 2.5 hours. The purpose of carbonization is to carbonize the binder precursor to form a binder.

本公开实施例的第三方面还提出一种负极活性材料,包括本公开实施例第一方面提出的硅碳复合材料。负极活性材料由该硅碳复合材料组成,也可继续添加其他成分构成组合物。The third aspect of the embodiment of the present disclosure also provides a negative active material, including the silicon-carbon composite material proposed in the first aspect of the embodiment of the present disclosure. The negative active material is composed of the silicon-carbon composite material, and other components can also be added to form the composition.

本公开实施例的第四方面还提出一种负极极片,负极极片可以包括负极集流体和设置于负极集流体上负极活性材料层,负极活性材料层可以包括本公开实施例的第三方面提出的负极活性材料、粘结剂和导电剂等。导电剂以及粘结剂的种类和含量不受具体的限制,可根据实际需求进行选择。负极集流体的种类也不受具体的限制,可根据实际需求进行选择,可以采用常规金属箔片,如铜箔。The fourth aspect of the embodiment of the present disclosure also provides a negative electrode sheet. The negative electrode sheet may include a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector. The negative electrode active material layer may include the third aspect of the embodiment of the present disclosure. Proposed negative active materials, binders and conductive agents, etc. The type and content of conductive agents and binders are not subject to specific restrictions and can be selected according to actual needs. The type of negative electrode current collector is not subject to specific restrictions and can be selected according to actual needs. Conventional metal foil, such as copper foil, can be used.

本公开实施例的第五方面还提出一种电化学装置,电化学装置例如可以是电池,包括正极极片、负极极片和隔离膜,负极极片为本公开实施例的第四方面提出的负极极片。用于与根据本公开实施例的负极极片配合使用的正极极片可以选用本领域常用的各种常规正极极片,其构成和制备方法是本领域公知的。用于本公开实施例的电池的隔膜可以选用本领域常用的各种隔膜。The fifth aspect of the embodiment of the present disclosure also provides an electrochemical device. The electrochemical device may be, for example, a battery, including a positive electrode sheet, a negative electrode sheet and a separator. The negative electrode sheet is the one proposed in the fourth aspect of the embodiment of the present disclosure. Negative pole piece. The positive electrode piece used in conjunction with the negative electrode piece according to the embodiment of the present disclosure can be selected from various conventional positive electrode pieces commonly used in the art, and their composition and preparation methods are well known in the art. The separator used in the battery of the embodiments of the present disclosure can be selected from various separators commonly used in the art.

本公开实施例的电池通常还包括电解液。可以选用本领域常用的各种电解液,例如电解质盐在非水溶剂中的溶液。例如,对于锂电池,可以使用电解质锂盐和非水溶剂的混合溶液。电解质锂盐可选自六氟磷酸锂(LiPF6)、高氯酸锂、四氟硼酸锂、六氟砷酸锂、卤化锂、氯铝酸锂、氟烃基磺酸锂中的一种或几种。有机溶剂可以选自链状碳酸酯、环状碳酸酯或它们组成的混合溶剂。其中,链状碳酸酯可以为碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)以及其他含氟、含硫或含不饱和键的链状有机酯类中的至少一种。环状碳酸酯可以为碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸亚乙烯酯(VC)、γ-丁内酯(γ-BL)、磺内酯以及其他含氟、含硫或含不饱和键的环状有机酯类中的一种或多种。Batteries of embodiments of the present disclosure generally further include an electrolyte. Various electrolytes commonly used in this field can be selected, such as solutions of electrolyte salts in non-aqueous solvents. For example, for lithium batteries, a mixed solution of electrolyte lithium salt and non-aqueous solvent can be used. The electrolyte lithium salt can be selected from one or more of lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium halide, lithium chloroaluminate, and lithium fluoroalkylsulfonate. The organic solvent can be selected from chain carbonates, cyclic carbonates or mixed solvents thereof. Among them, the chain carbonate can be dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other carbonates containing At least one of fluorine, sulfur-containing or unsaturated bond-containing chain organic esters. Cyclic carbonates can be ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), γ-butyrolactone (γ-BL), sultone and other fluorine-, sulfur- or One or more cyclic organic esters containing unsaturated bonds.

本公开实施例的电池可以为一次电池或二次电池。本公开实施例的电池可以是锂离子电池或钠离子电池,优选锂离子电池,例如可以为锂离子一次电池或锂离子二次电池。除了使用了如上所述的负极极片外,这些电池的构造和制备方法本身是公知的。并且根据本公开实施例的负极活性材料的制备方法简单,因此可以降低使用了根据本公开实施例的负极极片的电池的制造成本。本公开实施例的负极活性材料具有较高的比容量和电子导电率,内部穿插的碳纳米管导电网络降低了复合材料的阻抗、促进锂离子转移,提升了电极的倍率性能。The battery of the embodiment of the present disclosure may be a primary battery or a secondary battery. The battery in the embodiment of the present disclosure may be a lithium-ion battery or a sodium-ion battery, preferably a lithium-ion battery, and may be, for example, a lithium-ion primary battery or a lithium-ion secondary battery. Apart from the use of negative electrode plates as described above, the construction and preparation of these batteries are known per se. Moreover, the preparation method of the negative active material according to the embodiment of the present disclosure is simple, so the manufacturing cost of the battery using the negative electrode sheet according to the embodiment of the present disclosure can be reduced. The negative active material of the embodiment of the present disclosure has high specific capacity and electronic conductivity. The carbon nanotube conductive network interspersed inside reduces the impedance of the composite material, promotes lithium ion transfer, and improves the rate performance of the electrode.

本公开实施例的第六方面还提出一种电动车辆,该电动车辆装载有上述第五方面提出的电化学装置,具体的,电动车辆可以是任何需要电化学装置作为动力源的车辆,如电动公交车,轻轨电动车以及电动车等等。因其包括上述任一实施例的电化学装置,因而具有上述任一实施例电化学装置的有益效果。A sixth aspect of the embodiments of the present disclosure also provides an electric vehicle, which is loaded with the electrochemical device proposed in the fifth aspect. Specifically, the electric vehicle can be any vehicle that requires an electrochemical device as a power source, such as an electric vehicle. Buses, light rail electric vehicles and electric vehicles, etc. Because it includes the electrochemical device of any of the above embodiments, it has the beneficial effects of the electrochemical device of any of the above embodiments.

下面通过具体实施实例来进一步说明本公开的硅碳复合材料的制备方法。本领域技术人员应该明了,以下具体实施例仅仅是帮助理解本公开,不应视为对本公开的具体限制。The preparation method of the silicon-carbon composite material of the present disclosure will be further described below through specific implementation examples. Those skilled in the art should understand that the following specific examples are only to help understand the present disclosure and should not be regarded as specific limitations of the present disclosure.

本公开实施例硅碳复合材料的制备:Preparation of silicon-carbon composite materials in embodiments of the present disclosure:

S1、硅碳材料的制备方法:S1. Preparation method of silicon carbon material:

硅碳母粒No.1:称取5g纳米硅粉分散于50g甲苯中,超声分散后滴加入预热至900℃的化学气相反应炉中,保温1小时,制备得到硅碳母粒,硅碳母粒中硅元素的质量百分比含量为64%,粒径为1μm~5μm;Silicon carbon masterbatch No. 1: Weigh 5g of nano-silica powder and disperse it in 50g of toluene. After ultrasonic dispersion, add it dropwise into a chemical vapor phase reactor preheated to 900°C and keep it for 1 hour to prepare silicon carbon masterbatch. Silicon carbon The mass percentage content of silicon element in the masterbatch is 64%, and the particle size is 1μm~5μm;

硅碳母粒No.2:与硅碳母粒No.1的制备方法相同,区别在于液态碳源采用工业洗油;硅碳母粒中硅元素的质量百分比含量为45%,粒径为1μm~5μm;Silicon carbon masterbatch No.2: The preparation method is the same as silicon carbon masterbatch No.1, the difference is that the liquid carbon source uses industrial washing oil; the mass percentage of silicon element in the silicon carbon masterbatch is 45%, and the particle size is 1 μm ~5μm;

硅碳母粒No.3:与硅碳母粒No.1的制备方法相同,区别在于工业洗油为30g;硅碳母粒中硅元素的质量百分比含量为45%,粒径为1μm~5μm。Silicon carbon masterbatch No.3: The preparation method is the same as silicon carbon masterbatch No.1, the difference is that the industrial washing oil is 30g; the mass percentage of silicon element in the silicon carbon masterbatch is 45%, and the particle size is 1μm~5μm .

S2、按照重量比称取硅碳母粒、石墨化洋葱碳和石墨烯,具体添加比例如表1所示;倒入湿法造粒机中,先剪切搅拌5min,切割转速为2000rpm,混合转速为150rpm;然后滴加质量百分比浓度为10%的羧甲基纤维素钠水溶液,羧甲基纤维素钠水溶液的添加量为硅碳母粒、石墨材料和导电剂总质量的100%,剪切搅拌15min,切割转速为2000rpm,混合转速为150rpm。制备得到硅碳颗粒混合物,粒径控制在3μm~25μm之间。S2. Weigh the silicon carbon masterbatch, graphitized onion carbon and graphene according to the weight ratio. The specific addition ratio is shown in Table 1; pour into the wet granulator, cut and stir for 5 minutes, the cutting speed is 2000rpm, and mix The rotation speed is 150rpm; then add dropwise a carboxymethylcellulose sodium aqueous solution with a mass percentage concentration of 10%. The added amount of the carboxymethylcellulose sodium aqueous solution is 100% of the total mass of the silicon carbon masterbatch, graphite material and conductive agent. Shear Cut and stir for 15 minutes, the cutting speed is 2000rpm, and the mixing speed is 150rpm. A mixture of silicon-carbon particles is prepared, with the particle size controlled between 3 μm and 25 μm.

S3、将S2中制备的硅碳颗粒混合物在惰性气氛条件下,900℃~1000℃碳化保温2小时,获得硅碳复合材料。S3. Carbonize the silicon-carbon particle mixture prepared in S2 under inert atmosphere conditions at 900°C to 1000°C for 2 hours to obtain a silicon-carbon composite material.

表1Table 1

其中,粘结剂占硅碳复合材料总重的质量百分比采用TG热重分析进行测定。Among them, the mass percentage of the binder in the total weight of the silicon-carbon composite material was measured using TG thermogravimetric analysis.

其中,硅碳母粒1#的扫描电子显微照片如图2、图3所示。由图2、图3所示,明显看出大颗粒由小颗粒聚集而成,并且石墨烯分散在各组元之间形成导电碳网络,硅碳母粒也被紧密塑封于石墨材料的堆积空隙中。Among them, the scanning electron micrographs of silicon carbon masterbatch 1# are shown in Figures 2 and 3. As shown in Figures 2 and 3, it is obvious that large particles are aggregated from small particles, and graphene is dispersed between each component to form a conductive carbon network, and the silicon carbon masterbatch is also tightly sealed in the stacking gaps of the graphite material. middle.

硅碳复合材料8#:硅碳母粒、石墨化洋葱碳和碳纳米管与硅碳复合材料1#相同,区别在于:Silicon carbon composite material 8#: Silicon carbon masterbatch, graphitized onion carbon and carbon nanotubes are the same as silicon carbon composite material 1#, the difference is:

粘结剂前体溶液为质量百分比浓度为30%的羧甲基纤维素钠水溶液,粘结剂占硅碳复合材料总重量的20%。The binder precursor solution is a sodium carboxymethylcellulose aqueous solution with a mass percentage concentration of 30%, and the binder accounts for 20% of the total weight of the silicon-carbon composite material.

硅碳复合材料9#:硅碳母粒、石墨化洋葱碳和碳纳米管与硅碳复合材料1#相同,区别在于:粘结剂前体溶液为质量百分比浓度为2%的羧甲基纤维素钠水溶液,粘结剂占硅碳复合材料总重量的1%。Silicon carbon composite material 9#: silicon carbon masterbatch, graphitized onion carbon and carbon nanotubes are the same as silicon carbon composite material 1#, the difference is that the binder precursor solution is carboxymethyl fiber with a mass percentage concentration of 2% Sodium aqueous solution, the binder accounts for 1% of the total weight of the silicon-carbon composite material.

硅碳复合材料10#:硅碳母粒、石墨化洋葱碳和碳纳米管与硅碳复合材料1#相同,区别在于:按照重量比称取硅碳母粒、石墨化洋葱碳和碳纳米管后加入到大量的粘结剂前体溶液中搅拌混合制备成浆料,粘结剂前体溶液的添加量为硅碳母粒、石墨材料和导电剂总质量的600%;粘结剂前体溶液为质量百分比浓度为2%的羧甲基纤维素钠水溶液,烧结后粘结剂占硅碳复合材料总重量的5%,搅拌混合均匀后干燥、煅烧并粉碎。Silicon carbon composite material 10#: silicon carbon masterbatch, graphitized onion carbon and carbon nanotubes are the same as silicon carbon composite material 1#, the difference is: weigh the silicon carbon masterbatch, graphitized onion carbon and carbon nanotubes according to the weight ratio Then add it to a large amount of binder precursor solution, stir and mix to prepare a slurry. The amount of binder precursor solution added is 600% of the total mass of silicon carbon masterbatch, graphite material and conductive agent; binder precursor The solution is a sodium carboxymethylcellulose aqueous solution with a mass percentage concentration of 2%. After sintering, the binder accounts for 5% of the total weight of the silicon-carbon composite material. The mixture is stirred and mixed evenly, then dried, calcined and pulverized.

硅碳复合材料11#:硅碳母粒和碳纳米管与硅碳复合材料1#相同,区别在于石墨材料采用人造石墨,添加量也与硅碳复合材料1#相同。Silicon-carbon composite material 11#: Silicon-carbon masterbatch and carbon nanotubes are the same as silicon-carbon composite material 1#. The difference is that the graphite material uses artificial graphite, and the addition amount is also the same as silicon-carbon composite material 1#.

制备得到的硅碳复合材料的物理参数如表2:The physical parameters of the prepared silicon-carbon composite materials are as shown in Table 2:

其中,物理参数的检测方法根据激光粒度分析仪以及振实密度测试仪(振实次数:30000,频率:1次/秒)得到。Among them, the detection method of physical parameters is obtained by laser particle size analyzer and tap density tester (number of taps: 30000, frequency: 1 time/second).

表2Table 2

硅碳复合材料编号Silicon carbon composite material number 振实密度(g/cm3)Tap density (g/cm 3 ) 粒径(μm)Particle size (μm) 硅碳复合材料1#Silicon carbon composite material 1# 0.810.81 25~5025~50 硅碳复合材料2#Silicon carbon composite material 2# 0.800.80 15~5015~50 硅碳复合材料3#Silicon carbon composite material 3# 0.790.79 10~5010~50 硅碳复合材料4#Silicon carbon composite material 4# 0.950.95 30~8030~80 硅碳复合材料5#Silicon carbon composite material 5# 0.800.80 40~10040~100 硅碳复合材料6#Silicon carbon composite material 6# 0.840.84 30~6030~60 硅碳复合材料7#Silicon carbon composite material 7# 0.760.76 10~5010~50 硅碳复合材料8#Silicon carbon composite material 8# 0.800.80 50~15050~150 硅碳复合材料9#Silicon carbon composite material 9# 0.540.54 3~203~20 硅碳复合材料10#Silicon carbon composite material 10# 0.650.65 20~6020~60 硅碳复合材料11#Silicon carbon composite material 11# 0.750.75 20~5520~55

由表2可知,硅碳复合材料1#~5#均获得了较高的振实密度和能量密度。而硅碳复合材料6#中由于硅碳母粒的添加量过小,因此其能量密度有所减弱。硅碳复合材料7#中由于石墨材料的添加量过小,因此其振实密度有所降低。硅碳复合材料8#中由于粘结剂比例过大,因此其粒径较大不利于颗粒密排堆积,且振实密度和能量密度均有所降低。硅碳复合材料9#由于粘结剂比例过小,因此其粒径较小,振实密度较小。It can be seen from Table 2 that silicon-carbon composite materials 1# to 5# have obtained higher tap density and energy density. In silicon-carbon composite material 6#, because the amount of silicon-carbon masterbatch added is too small, its energy density is weakened. Since the added amount of graphite material in silicon-carbon composite material 7# is too small, its tap density is reduced. Since the proportion of binder in silicon-carbon composite material 8# is too large, its larger particle size is not conducive to close-packed particle packing, and the tap density and energy density are both reduced. Silicon-carbon composite material 9# has a smaller particle size and smaller tap density because the proportion of binder is too small.

本公开实施例材料的性能测定:Performance measurement of materials according to the embodiments of the present disclosure:

(1)半电池测试(1) Half cell test

将负极活性材料1#~11#作为锂离子电池负极组装成扣式电池,负极活性材料1#~11#一一对应前述硅碳复合材料1#~11#。The negative active materials 1# to 11# are used as negative electrodes of lithium ion batteries to assemble a button battery. The negative active materials 1# to 11# correspond to the aforementioned silicon carbon composite materials 1# to 11# one by one.

具体制备方法为:将负极活性材料1#~11#、羧甲基纤维素钠、乙炔黑按质量比为91:6:3混合,研磨均匀后加适量水继续研磨制备电极浆料,将浆料均匀涂覆在涂碳铜箔上,在120℃下真空干燥12h,制得电极片1#~11#。将锂片为对电极,组装成半电池1#~12#,在LAND(CT3001A)电池测试系统,以200mA/g的电流密度进行充放电性能测试,测试结果如图4和表3所示:The specific preparation method is: mix the negative active materials 1# to 11#, sodium carboxymethyl cellulose, and acetylene black in a mass ratio of 91:6:3, grind them evenly, add an appropriate amount of water, and continue grinding to prepare the electrode slurry. The material is evenly coated on the carbon-coated copper foil, and vacuum dried at 120°C for 12 hours to prepare electrode sheets 1#~11#. Use the lithium sheet as the counter electrode and assemble it into half cells 1#~12#. In the LAND (CT3001A) battery test system, the charge and discharge performance is tested at a current density of 200mA/g. The test results are shown in Figure 4 and Table 3:

表3table 3

从表3可以看出,采用负极活性材料1#~5#作为负极时具有较高的容量,明显过于传统石墨材料,并且拥有较高的首次库伦效率。同时,在循环100周后,半电池1#~5#具有90%左右的容量保持率,说明硅碳负极材料具有稳定的循环性能。而半电池6#、8#的电池容量有所减弱。半电池7#、9#中的容量保持率有所降低。半电池中的电池由于粘结剂比例过大,因此其粒径较大,且振实密度和能量密度均有所降低。硅碳复合材料9#由于粘结剂比例过小,因此其粒径较小,密度较大。It can be seen from Table 3 that when using negative active materials 1# to 5# as the negative electrode, it has a higher capacity, which is obviously better than traditional graphite materials, and has a higher first Coulombic efficiency. At the same time, after 100 cycles, half cells 1# to 5# have a capacity retention rate of about 90%, indicating that the silicon carbon anode material has stable cycle performance. The battery capacity of half-battery 6# and 8# has been weakened. The capacity retention rate in half cells 7# and 9# has decreased. The battery in the half-cell has a larger particle size due to an excessive proportion of binder, and the tap density and energy density are reduced. Silicon-carbon composite material 9# has a smaller particle size and a larger density because the binder ratio is too small.

(2)全电池测试(2) Full battery test

将负极活性材料1#~11#作为负极材料,负极活性材料1#~11#一一对应前述硅碳复合材料1#~11#,以磷酸铁锂为正极,组装成扣式全电池1#~11#。使用LAND电池测试系统对组装的全电池进行测试。Use negative active materials 1#~11# as negative electrode materials, negative active materials 1#~11# correspond to the aforementioned silicon carbon composite materials 1#~11# one by one, use lithium iron phosphate as the positive electrode, and assemble into a button full battery 1# ~11#. The assembled full battery is tested using the LAND battery testing system.

测试循环性能:充放电电流密度2C,电压范围2.5V~3.65V,循环次数300次。Test cycle performance: charge and discharge current density 2C, voltage range 2.5V ~ 3.65V, number of cycles 300 times.

测试倍率性能:充放电电流密度为0.1C、0.2C、0.5C、1C、2C、5C,电压范围2.5V~3.65V。结果如图5和表4所示:Test rate performance: charge and discharge current density is 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, voltage range is 2.5V~3.65V. The results are shown in Figure 5 and Table 4:

表4Table 4

从表4可知,本公开实施例的硅碳复合材料组装成全电池后拥有优秀的倍率性能和循环稳定性,本公开实施例制备的硅碳材料具有稳定的结构,石墨将硅碳母粒限域在堆积的空隙中可以有效抑制硅的体积膨胀,同时复合材料内部的碳纳米管网络促进了电子的转移和锂离子的扩散,从而提升其倍率充放电性能。而根据全电池5#、7#可知,如果石墨材料的添加量过小,倍率性能和循环稳定性均有所下降。全电池9#的倍率性能发生较大下降。As can be seen from Table 4, the silicon-carbon composite materials of the embodiments of the present disclosure have excellent rate performance and cycle stability after being assembled into a full battery. The silicon-carbon materials prepared by the embodiments of the present disclosure have a stable structure. The graphite limits the silicon-carbon masterbatch. The volume expansion of silicon can be effectively suppressed in the stacked gaps. At the same time, the carbon nanotube network inside the composite material promotes the transfer of electrons and the diffusion of lithium ions, thus improving its rate charge and discharge performance. According to full cells 5# and 7#, if the amount of graphite material added is too small, the rate performance and cycle stability will decrease. The rate performance of full battery 9# dropped significantly.

需要说明的是,在本文中,诸如“第一”和“第二”等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下,由语句“包括一个……”限定的要素,并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。It should be noted that, in this article, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

以上所述仅是本公开的具体实施方式,使本领域技术人员能够理解或实现本公开。对这些实施例的多种修改对本领域的技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本公开的精神或范围的情况下,在其它实施例中实现。因此,本公开将不会被限制于本文所述的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above descriptions are only specific embodiments of the present disclosure, enabling those skilled in the art to understand or implement the present disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be practiced in other embodiments without departing from the spirit or scope of the disclosure. Therefore, the present disclosure is not to be limited to the embodiments described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (14)

1.一种硅碳复合材料,其特征在于,包括石墨材料以及固定于所述石墨材料间的空隙中的硅碳材料。1. A silicon-carbon composite material, characterized in that it includes a graphite material and a silicon-carbon material fixed in the gaps between the graphite materials. 2.根据权利要求1所述的硅碳复合材料,其特征在于,所述硅碳材料为核壳结构,所述硅碳材料的内核为纳米硅,所述硅碳材料的外壳为碳层;和/或,所述硅碳材料为硅碳母粒,所述硅碳母粒的粒径为1μm~5μm。2. The silicon-carbon composite material according to claim 1, characterized in that the silicon-carbon material has a core-shell structure, the core of the silicon-carbon material is nano-silicon, and the outer shell of the silicon-carbon material is a carbon layer; And/or, the silicon carbon material is silicon carbon masterbatch, and the particle size of the silicon carbon masterbatch is 1 μm to 5 μm. 3.根据权利要求1所述的硅碳复合材料,其特征在于,所述石墨材料和所述硅碳材料两者形成硅碳复合颗粒,所述硅碳复合颗粒的粒径为10μm~80μm。3. The silicon-carbon composite material according to claim 1, wherein the graphite material and the silicon-carbon material form silicon-carbon composite particles, and the particle size of the silicon-carbon composite particles is 10 μm to 80 μm. 4.根据权利要求1所述的硅碳复合材料,其特征在于,所述硅碳材料中硅元素的质量百分比含量为20%~60%;和/或,4. The silicon-carbon composite material according to claim 1, characterized in that the mass percentage content of silicon element in the silicon-carbon material is 20% to 60%; and/or, 所述硅碳复合材料中所述硅碳材料的质量百分比含量为20%~50%;The mass percentage content of the silicon carbon material in the silicon carbon composite material is 20% to 50%; 所述硅碳复合材料中所述石墨材料的质量百分比含量为48%~79%。The mass percentage content of the graphite material in the silicon-carbon composite material is 48% to 79%. 5.根据权利要求3~4任一项所述的硅碳复合材料,其特征在于,所述硅碳复合材料中还包括导电剂,所述导电剂穿插于所述硅碳材料和所述石墨材料之间,用于在所述硅碳复合材料内部形成导电网络,优选地,所述硅碳复合材料中所述导电剂的质量百分比含量为1%~2%;5. The silicon-carbon composite material according to any one of claims 3 to 4, characterized in that the silicon-carbon composite material further includes a conductive agent, and the conductive agent is interspersed between the silicon-carbon material and the graphite. between materials, used to form a conductive network inside the silicon-carbon composite material. Preferably, the mass percentage content of the conductive agent in the silicon-carbon composite material is 1% to 2%; 所述硅碳复合材料中还包括粘结剂,所述硅碳材料与所述石墨材料之间、所述石墨材料之间通过粘合剂连接,所述硅碳复合颗粒之间通过粘合剂连接,优选地,所述粘合剂占所述硅碳复合材料总重量的2%~20%。The silicon carbon composite material also includes a binder. The silicon carbon material and the graphite material and the graphite materials are connected through an adhesive. The silicon carbon composite particles are connected through an adhesive. For connection, preferably, the adhesive accounts for 2% to 20% of the total weight of the silicon-carbon composite material. 6.根据权利要求5所述的硅碳复合材料,其特征在于,所述导电剂选自碳纳米材料,优选地,所述碳纳米材料选自零维、一维、二维和三维碳纳米材料中的至少一种;6. The silicon-carbon composite material according to claim 5, characterized in that the conductive agent is selected from carbon nanomaterials. Preferably, the carbon nanomaterials are selected from zero-dimensional, one-dimensional, two-dimensional and three-dimensional carbon nanomaterials. at least one of the materials; 所述石墨材料包括石墨和类石墨材料中的至少一种,所述石墨选自人造石墨和天然石墨中的至少一种;所述类石墨材料选自洋葱状碳微球和MCMB中的至少一种;优选地,所述石墨材料的粒径为1μm~25μm。The graphite material includes at least one of graphite and graphite-like materials, the graphite is selected from at least one of artificial graphite and natural graphite; the graphite-like material is selected from at least one of onion-like carbon microspheres and MCMB. species; preferably, the particle size of the graphite material is 1 μm to 25 μm. 7.根据权利要求1~6中任一项所述的硅碳复合材料,其特征在于,所述硅碳复合材料的振实密度为0.4~0.6g/cm3,所述硅碳复合材料的储锂容量为400~2000mAh/g。7. The silicon-carbon composite material according to any one of claims 1 to 6, characterized in that the tap density of the silicon-carbon composite material is 0.4-0.6 g/cm 3 , and the tap density of the silicon-carbon composite material is 0.4-0.6 g/cm 3 . The lithium storage capacity is 400~2000mAh/g. 8.如权利要求5~7任一项所述硅碳复合材料的制备方法,其特征在于,至少包括以下步骤:8. The preparation method of silicon-carbon composite material according to any one of claims 5 to 7, characterized in that it at least includes the following steps: S1、制备所述硅碳材料;S1. Prepare the silicon carbon material; S2、取所述硅碳材料、所述石墨材料和所述导电剂,混合均匀,加入粘结剂前体溶液后继续混合;S2. Take the silicon carbon material, the graphite material and the conductive agent, mix them evenly, add the binder precursor solution and continue mixing; S3、将混合后的原料在惰性气氛条件下碳化,得到所述硅碳复合材料。S3. Carbonize the mixed raw materials under inert atmosphere conditions to obtain the silicon-carbon composite material. 9.根据权利要求8所述的制备方法,其特征在于,9. The preparation method according to claim 8, characterized in that, 在S1中,将纳米硅分散于液态碳源中,获得分散液,将所述分散液在惰性气氛下热解并保温,即得所述硅碳材料,优选地,所述液态碳源选自链状烃、环状烃或混合烃;和/或,In S1, nano-silicon is dispersed in a liquid carbon source to obtain a dispersion. The dispersion is pyrolyzed and kept warm under an inert atmosphere to obtain the silicon carbon material. Preferably, the liquid carbon source is selected from Chain hydrocarbons, cyclic hydrocarbons or mixed hydrocarbons; and/or, 在S2中,取所述硅碳材料、所述石墨材料和所述导电剂先在湿法造粒机中混合5~10分钟,切割转速为1500~2500rpm,混合转速为120~180rpm;然后加入粘结剂前体溶液再搅拌10~30分钟,切割转速为1500~2500rpm,混合转速为120~180rpm;和/或,In S2, take the silicon carbon material, the graphite material and the conductive agent and mix them in a wet granulator for 5 to 10 minutes, with a cutting speed of 1500 to 2500 rpm and a mixing speed of 120 to 180 rpm; then add The binder precursor solution is stirred for another 10 to 30 minutes, the cutting speed is 1500-2500rpm, and the mixing speed is 120-180rpm; and/or, 在S3中,所述碳化的温度为600℃~1200℃,所述碳化的时间为1~3小时。In S3, the carbonization temperature is 600°C to 1200°C, and the carbonization time is 1 to 3 hours. 10.根据权利要求8所述的制备方法,其特征在于,在S2中,所述粘结剂前体溶液中溶质的质量百分比浓度为2%~30%,所述粘结剂前体溶液的添加量为硅碳材料、石墨材料和导电剂总质量的20%~120%;10. The preparation method according to claim 8, characterized in that, in S2, the mass percentage concentration of the solute in the binder precursor solution is 2% to 30%, and the concentration of the solute in the binder precursor solution is 2% to 30%. The added amount is 20% to 120% of the total mass of silicon carbon materials, graphite materials and conductive agents; 优选的,所述粘结剂前体溶液选自水性粘结剂或油性粘结剂;更优选地,所述水性粘结剂选自羧甲基纤维素钠水溶液、海藻酸钠水溶液、聚丙烯酸水溶液中的至少一种;更优选地,所述油性粘结剂选自聚偏氟乙烯/N,N-二甲基甲酰胺溶液、沥青-吡啶混合物、沥青-四氢呋喃混合物中的至少一种。Preferably, the binder precursor solution is selected from an aqueous binder or an oily binder; more preferably, the aqueous binder is selected from at least one of a sodium carboxymethyl cellulose aqueous solution, a sodium alginate aqueous solution, and a polyacrylic acid aqueous solution; more preferably, the oily binder is selected from at least one of a polyvinylidene fluoride/N,N-dimethylformamide solution, an asphalt-pyridine mixture, and an asphalt-tetrahydrofuran mixture. 11.一种负极活性材料,包括如权利要求1~7任一项所述的硅碳复合材料或如权利要求8~10任一项所述的制备方法制得的硅碳复合材料。11. A negative active material, including the silicon-carbon composite material according to any one of claims 1 to 7 or the silicon-carbon composite material prepared by the preparation method according to any one of claims 8 to 10. 12.一种负极极片,其特征在于,所述负极极片中的负极活性材料选自如权利要求11所述的负极活性材料。12. A negative electrode sheet, characterized in that the negative active material in the negative electrode sheet is selected from the negative active materials as claimed in claim 11. 13.一种电化学装置,包括正极极片、负极极片和隔离膜,其特征在于,所述负极极片为权利要求12所述的负极极片。13. An electrochemical device, comprising a positive electrode piece, a negative electrode piece and an isolation film, wherein the negative electrode piece is the negative electrode piece according to claim 12. 14.一种车辆,其特征在于,所述车辆中包含如权利要求13所述的电化学装置。14. A vehicle, characterized in that the electrochemical device according to claim 13 is included in the vehicle.
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