CN111916745A - Silicon negative electrode material, preparation method thereof and electrochemical cell - Google Patents

Silicon negative electrode material, preparation method thereof and electrochemical cell Download PDF

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CN111916745A
CN111916745A CN202010765493.3A CN202010765493A CN111916745A CN 111916745 A CN111916745 A CN 111916745A CN 202010765493 A CN202010765493 A CN 202010765493A CN 111916745 A CN111916745 A CN 111916745A
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何向明
王莉
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Abstract

本发明公开了一种硅负极材料,所述硅负极材料为二次复合颗粒,所述二次复合颗粒包括硅颗粒、导电剂以及热固性高分子聚合物,所述热固性高分子聚合物至少设置在所述二次复合颗粒的外层。本发明公开了一种硅负极材料的制备方法。本发明还公开了一种电化学电池。

Figure 202010765493

The invention discloses a silicon negative electrode material. The silicon negative electrode material is secondary composite particles. The secondary composite particles include silicon particles, a conductive agent and a thermosetting polymer. The thermosetting polymer is arranged at least in the outer layer of the secondary composite particles. The invention discloses a preparation method of a silicon negative electrode material. The invention also discloses an electrochemical cell.

Figure 202010765493

Description

硅负极材料及其制备方法,以及电化学电池Silicon anode material and preparation method thereof, and electrochemical cell

技术领域technical field

本发明涉及电池技术领域,特别是涉及一种硅负极材料及其制备方法,以及电化学电池。The invention relates to the technical field of batteries, in particular to a silicon negative electrode material and a preparation method thereof, and an electrochemical battery.

背景技术Background technique

目前商业化的负极材料主要是石墨,其具有理论比容量较低,高倍率充放电性能差等缺点已不可能完全满足锂离子电池发展的需求,高能动力型锂离子电池的发展迫切需要寻求高容量、长寿命、安全可靠的新型高容量负极来替代石墨类碳负极。At present, the commercialized negative electrode material is mainly graphite, which has the disadvantages of low theoretical specific capacity and poor high-rate charge-discharge performance. It is impossible to fully meet the needs of the development of lithium-ion batteries. A new type of high-capacity negative electrode with high capacity, long life, safe and reliable to replace the graphite-like carbon negative electrode.

硅负极材料有较高的理论比容量,低的脱嵌锂电位,是一种非常有发展前景的高容量负极材料。目前限制硅负极应用的主要问题是在电池充放电过程中硅会发生体积变化,从而导致电池性能的下降。Silicon anode material has high theoretical specific capacity and low lithium-deintercalation potential, and is a very promising high-capacity anode material. The main problem that currently restricts the application of silicon anodes is that the volume of silicon will change during the charging and discharging process of the battery, which will lead to the decline of the battery performance.

发明内容SUMMARY OF THE INVENTION

基于此,有必要提供一种新型硅负极材料及其制备方法,以及电化学电池。Based on this, it is necessary to provide a new type of silicon anode material and its preparation method, as well as an electrochemical cell.

一种硅负极材料,所述硅负极材料为二次复合颗粒,所述二次复合颗粒包括硅颗粒、导电剂以及热固性高分子聚合物,所述热固性高分子聚合物至少设置在所述二次复合颗粒的外层。A silicon negative electrode material, the silicon negative electrode material is secondary composite particles, the secondary composite particles include silicon particles, a conductive agent and a thermosetting high molecular polymer, and the thermosetting high molecular polymer is arranged at least on the secondary composite particles. The outer layer of the composite particle.

在其中一个实施例中,所述硅负极材料为核壳结构,所述热固性高分子聚合物在所述核壳结构的壳层均匀连续设置,所述硅颗粒在所述核壳结构的核心内。In one embodiment, the silicon negative electrode material is a core-shell structure, the thermosetting polymer is uniformly and continuously arranged in the shell layer of the core-shell structure, and the silicon particles are in the core of the core-shell structure .

在其中一个实施例中,所述核壳结构的所述壳层的致密性大于所述核心的致密性。In one embodiment, the density of the shell layer of the core-shell structure is greater than the density of the core.

在其中一个实施例中,所述热固性高分子材料选自羧甲基纤维素钠和聚丙烯酸的交联聚合物、环氧树脂、酚醛树脂、聚氨酯、聚酰胺及聚酰亚胺中的一种或多种。In one embodiment, the thermosetting polymer material is selected from a cross-linked polymer of sodium carboxymethyl cellulose and polyacrylic acid, epoxy resin, phenolic resin, polyurethane, polyamide and polyimide or more.

在其中一个实施例中,所述导电剂选自活性炭、石墨烯、碳纳米管、科琴黑、SuperP、乙炔黑及石墨中的一种或多种。In one embodiment, the conductive agent is selected from one or more of activated carbon, graphene, carbon nanotubes, Ketjen black, SuperP, acetylene black and graphite.

在其中一个实施例中,所述硅颗粒、所述导电剂以及所述热固性高分子聚合物的质量比为(30~50):(1~20):(4~10)。In one embodiment, the mass ratio of the silicon particles, the conductive agent and the thermosetting polymer is (30-50):(1-20):(4-10).

在其中一个实施例中,所述二次复合颗粒的粒径为5μm~100μm。In one embodiment, the particle size of the secondary composite particles is 5 μm˜100 μm.

一种所述的硅负极材料的制备方法,包括:A preparation method of the described silicon anode material, comprising:

将所述硅颗粒、所述导电剂和热固性高分子聚合物单体在溶剂中混合形成分散液;mixing the silicon particles, the conductive agent and the thermosetting polymer monomer in a solvent to form a dispersion;

将所述分散液进行喷雾干燥形成硅负极材料前体颗粒。The dispersion liquid is spray-dried to form silicon anode material precursor particles.

在其中一个实施例中,所述喷雾干燥的温度为50℃~400℃。In one embodiment, the temperature of the spray drying is 50°C to 400°C.

一种电化学电池,包括正极、负极及电解质,所述负极包括所述的硅负极材料。以及An electrochemical cell includes a positive electrode, a negative electrode and an electrolyte, and the negative electrode includes the silicon negative electrode material. as well as

将所述硅负极材料前体颗粒进行加热,使所述热固性高分子聚合物单体交联聚合为所述热固性高分子聚合物。The silicon anode material precursor particles are heated to cross-link and polymerize the thermosetting polymer monomer into the thermosetting polymer.

本发明所述硅负极材料中,所述热固性高分子聚合物不经碳化,直接与硅颗粒硅的一次颗粒及所述导电剂形成二次复合颗粒,利用所述热固性高分子聚合物兼具的强度和韧性,对硅颗粒的体积进行限制的同时,避免因硅颗粒体积变化导致的二次复合颗粒破裂,使所述二次复合颗粒的形状和结构在充放电循环过程中具有较好的稳定性和完整性,从而使得电化学电池具有更好的电化学性能。In the silicon negative electrode material of the present invention, the thermosetting macromolecular polymer directly forms secondary composite particles with the primary particles of silicon particles and the conductive agent without carbonization. Strength and toughness, while limiting the volume of silicon particles, avoiding the rupture of the secondary composite particles caused by the volume change of the silicon particles, so that the shape and structure of the secondary composite particles have better stability during the charge-discharge cycle. properties and integrity, so that the electrochemical cell has better electrochemical performance.

附图说明Description of drawings

图1为本发明一实施例的硅负极材料的制备方法流程示意图;1 is a schematic flowchart of a method for preparing a silicon negative electrode material according to an embodiment of the present invention;

图2A、图2B为本发明实施例1硅负极材料产品的扫描电镜照片。FIG. 2A and FIG. 2B are scanning electron microscope photographs of the silicon anode material product in Example 1 of the present invention.

具体实施方式Detailed ways

为了使本发明的目的、技术方案及优点更加清楚明白,以下通过实施例,并结合附图,对本发明的硅负极材料及其制备方法,以及电化学电池进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。In order to make the purpose, technical solutions and advantages of the present invention clearer, the following examples and the accompanying drawings will further describe the silicon negative electrode material and the preparation method thereof, as well as the electrochemical cell of the present invention. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

本发明实施例提供一种硅负极材料,所述硅负极材料为二次复合颗粒,所述二次复合颗粒包括硅颗粒、导电剂以及热固性高分子聚合物,所述热固性高分子聚合物至少设置在所述二次复合颗粒的外层。An embodiment of the present invention provides a silicon negative electrode material, the silicon negative electrode material is secondary composite particles, and the secondary composite particles include silicon particles, a conductive agent and a thermosetting polymer, and the thermosetting polymer is at least set in the outer layer of the secondary composite particles.

传统的硅负极材料中多采用将碳源热解形成碳单质,与硅复合形成硅碳复合材料,但发明人通过研究发现高温热解后得到的碳具有较大的脆性,在电池充放电过程中硅发生体积变化容易导致硅碳复合颗粒破裂,外部表现为电池的充放电循环性能随循环次数增加而下降。本发明实施例所述硅负极材料中,所述热固性高分子聚合物不经碳化,直接与硅的一次颗粒及所述导电剂形成二次复合颗粒,利用所述热固性高分子聚合物兼具的强度和韧性,对硅颗粒的体积进行限制的同时,避免因硅颗粒体积变化导致的二次复合颗粒破裂,使所述二次复合颗粒的形状和结构在充放电循环过程中具有较好的稳定性和完整性,从而使得电化学电池具有更好的电化学性能。In traditional silicon anode materials, carbon source is pyrolyzed to form carbon element, which is compounded with silicon to form silicon-carbon composite material. The volume change of the medium silicon easily leads to the rupture of the silicon-carbon composite particles, and the external manifestation is that the charge-discharge cycle performance of the battery decreases with the increase of the number of cycles. In the silicon negative electrode material according to the embodiment of the present invention, the thermosetting high molecular polymer directly forms secondary composite particles with the primary silicon particles and the conductive agent without carbonization. Strength and toughness, while limiting the volume of silicon particles, avoiding the rupture of the secondary composite particles caused by the volume change of the silicon particles, so that the shape and structure of the secondary composite particles have better stability during the charge-discharge cycle. properties and integrity, so that the electrochemical cell has better electrochemical performance.

所述热固性高分子聚合物为三维交联网络,具有不溶不熔的性质。所述热固性高分子聚合物可以由热固性高分子聚合物的单体经加热交联聚合而成,一旦所述热固性高分子聚合物加工交联成型后不能再次加工,形状不再发生改变,且具有较好的强度和韧性,能够在电化学电池充放电过程中保持固有的形状和结构,起到支撑所述二次复合颗粒的作用。在一实施例中,所述热固性高分子聚合物可以选自热固性树脂。在一些实施例中,所述热固性树脂可以选自羧甲基纤维素钠(CMC)和聚丙烯酸(PAA)的交联聚合物、环氧树脂、酚醛树脂、聚氨酯、聚酰胺及聚酰亚胺中的一种或多种。The thermosetting macromolecular polymer is a three-dimensional cross-linked network with insoluble and infusible properties. The thermosetting macromolecular polymer can be obtained by cross-linking and polymerizing the monomers of the thermosetting macromolecular polymer. Once the thermosetting macromolecular polymer is processed and cross-linked, it cannot be processed again, the shape will not change, and it has Good strength and toughness can maintain the inherent shape and structure during the charging and discharging process of the electrochemical cell, and play the role of supporting the secondary composite particles. In one embodiment, the thermosetting polymer can be selected from thermosetting resins. In some embodiments, the thermosetting resin may be selected from cross-linked polymers of sodium carboxymethyl cellulose (CMC) and polyacrylic acid (PAA), epoxy resins, phenolic resins, polyurethanes, polyamides, and polyimides one or more of.

在一实施例中,所述硅颗粒、所述导电剂和所述热固性高分子聚合物可以均匀混合。所述热固性高分子聚合物设置在所述二次复合颗粒的外层和内部,分布在所述硅颗粒和所述导电剂之间。所述热固性高分子聚合物在所述二次复合颗粒中形成牢固的网状支架,所述硅颗粒和所述导电剂分散在所述网状支架的间隙中,所述网状支架支撑和维持所述硅颗粒和所述导电剂的结构,使电化学电池的负极在脱嵌离子的过程中保持结构稳定。并且所述热固性高分子聚合物均匀分布在所述二次复合颗粒中,使所述二次复合颗粒保持整体均一性,有利于保持电化学电池的导电稳定性。In one embodiment, the silicon particles, the conductive agent and the thermosetting polymer may be uniformly mixed. The thermosetting macromolecular polymer is arranged on the outer layer and inside of the secondary composite particles, and is distributed between the silicon particles and the conductive agent. The thermosetting macromolecular polymer forms a firm mesh scaffold in the secondary composite particles, the silicon particles and the conductive agent are dispersed in the gaps of the mesh scaffold, and the mesh scaffold supports and maintains The structures of the silicon particles and the conductive agent keep the structure of the negative electrode of the electrochemical cell stable during the process of deintercalating ions. In addition, the thermosetting macromolecular polymer is uniformly distributed in the secondary composite particles, so that the secondary composite particles maintain overall uniformity, which is beneficial to maintain the electrical conductivity stability of the electrochemical cell.

在另一实施例中,所述硅负极材料为核壳结构,所述核壳结构可以包括壳层和核心。所述核壳结构的壳层包括所述热固性高分子聚合物,所述热固性高分子聚合物可以在所述壳层均匀连续设置,所述硅颗粒可以包覆位于所述核壳结构核心。所述导电剂可与所述热固性高分子聚合物及所述硅颗粒均匀混合,即分布在整个二次复合颗粒中。在一实施例中,所述核心中也包括一定量的所述热固性高分子聚合物,与所述硅颗粒和所述导电剂混合。In another embodiment, the silicon anode material is a core-shell structure, and the core-shell structure may include a shell layer and a core. The shell layer of the core-shell structure includes the thermosetting macromolecular polymer, the thermosetting macromolecular polymer can be uniformly and continuously arranged in the shell layer, and the silicon particles can cover the core of the core-shell structure. The conductive agent can be uniformly mixed with the thermosetting polymer and the silicon particles, that is, distributed throughout the secondary composite particles. In one embodiment, the core also includes a certain amount of the thermosetting polymer, which is mixed with the silicon particles and the conductive agent.

在一实施例中,所述核壳结构的所述壳层的致密性大于核心的致密性,核心具有一定孔隙。所述二次复合颗粒可以通过喷雾干燥制造,在喷雾干燥的过程中,二次复合颗粒的表层可先被干燥而“结皮”,从而使二次复合颗粒从外部被定型,内部在后续干燥过程中形成的孔隙被保留,形成壳层密实而核心疏松的结构。密实的壳层可以保护所述硅颗粒锂化(或钠化、镁化)后不与电解液反应,酥松的核可以为硅颗粒的体积膨胀提供缓冲,进一步保护所述二次复合颗粒不发生破裂,从而使得所述二次复合颗粒具有很好的电化学性能。In one embodiment, the density of the shell layer of the core-shell structure is greater than the density of the core, and the core has certain pores. The secondary composite particles can be produced by spray drying. In the process of spray drying, the surface layer of the secondary composite particles can be dried and "skinned" first, so that the secondary composite particles can be shaped from the outside, and the interior is subsequently dried. The pores formed during the process are retained, forming a structure with a dense shell and a loose core. The dense shell layer can protect the silicon particles from reacting with the electrolyte after lithiation (or sodiumization or magnesiumization), and the crisp core can provide buffers for the volume expansion of the silicon particles, further protecting the secondary composite particles from occurring fracture, so that the secondary composite particles have good electrochemical performance.

在一实施例中,所述导电剂可以选自锂离子电池中常用的导电剂,包括但不限于活性炭、石墨烯、碳纳米管、科琴黑、Super P、乙炔黑及石墨中的一种或多种。In one embodiment, the conductive agent can be selected from the conductive agents commonly used in lithium-ion batteries, including but not limited to one of activated carbon, graphene, carbon nanotubes, Ketjen black, Super P, acetylene black and graphite. or more.

在一实施例中,所述硅颗粒、所述导电剂以及所述热固性高分子聚合物的质量比可以为(30~50):(1~20):(4~10)。所述硅颗粒的质量可以占所述二次复合颗粒总质量的30%~50%,所述导电剂的质量可以占所述二次复合颗粒总质量的1%~20%,所述热固性高分子聚合物的质量可以占所述二次复合颗粒总质量的4%~10%。优选的,所述固性高分子聚合物的质量可以占所述二次复合颗粒总质量的5%~7%。In one embodiment, the mass ratio of the silicon particles, the conductive agent and the thermosetting polymer may be (30-50):(1-20):(4-10). The mass of the silicon particles may account for 30% to 50% of the total mass of the secondary composite particles, the mass of the conductive agent may account for 1% to 20% of the total mass of the secondary composite particles, and the thermosetting properties are high. The mass of the molecular polymer may account for 4% to 10% of the total mass of the secondary composite particles. Preferably, the mass of the solid macromolecular polymer may account for 5% to 7% of the total mass of the secondary composite particles.

在一实施例中,所述二次复合颗粒的粒径可以为5μm~100μm。优选的,所述二次复合颗粒的粒径可以为6μm~20μm。所述硅颗粒的粒径可以为10nm~500nm。所述硅颗粒可以为颗粒状的单质硅。In one embodiment, the particle size of the secondary composite particles may be 5 μm˜100 μm. Preferably, the particle size of the secondary composite particles may be 6 μm˜20 μm. The particle size of the silicon particles may be 10 nm˜500 nm. The silicon particles may be granular elemental silicon.

请参阅图1,本发明实施例还提供一种所述硅负极材料的制备方法,包括:Referring to FIG. 1, an embodiment of the present invention also provides a method for preparing the silicon anode material, including:

S10,将所述硅颗粒、所述导电剂和热固性高分子聚合物单体在溶剂中混合形成分散液;S10, mixing the silicon particles, the conductive agent and the thermosetting polymer monomer in a solvent to form a dispersion;

S20,将所述分散液进行喷雾干燥形成硅负极材料前体颗粒。S20, spray-drying the dispersion to form silicon anode material precursor particles.

本发明实施例通过喷雾干燥的方式形成硅负极材料前体颗粒,通过进一步的加热交联,使硅负极材料前体颗粒中的热固性高分子聚合物单体交联形成具有三维网络结构的热固性高分子聚合物。In the embodiment of the present invention, the silicon anode material precursor particles are formed by spray drying, and the thermosetting macromolecular polymer monomer in the silicon anode material precursor particles is cross-linked by further heating and cross-linking to form a three-dimensional network structure. molecular polymers.

所述步骤S10还可包括将其他添加助剂,例如固化剂混合在所述分散液中的步骤。所述固化剂的种类与所述热固性高分子聚合物单体的种类相互匹配。在一实施例中,所述热固性高分子聚合物单体为环氧树脂单体,所述固化剂可以选自脂肪胺、脂环胺、芳香胺、聚酰胺、酸酐、树脂类及叔胺中的至少一种。The step S10 may further include the step of mixing other additives, such as a curing agent, into the dispersion. The type of the curing agent is matched with the type of the thermosetting polymer monomer. In one embodiment, the thermosetting polymer monomer is an epoxy resin monomer, and the curing agent can be selected from aliphatic amines, alicyclic amines, aromatic amines, polyamides, acid anhydrides, resins and tertiary amines at least one of.

所述溶剂可以包括不与所述热固性高分子聚合物单体发生化学反应的易挥发有机溶剂。所述易挥发有机溶剂可以选自但不限于N-甲基吡咯烷酮(NMP)、甲醇、乙醇、乙二醇、丙醇、异丙醇、乙腈、丙酮、乙醚、N,N二甲基甲酰胺(DMF)、N,N二甲基乙酰胺(DMAc)及四氢呋喃(THF)中的一种或一种以上。所述硅颗粒、所述导电剂以及所述热固性高分子聚合物单体的质量比可以为(30~50):(1~20):(4~10),根据所述硅负极材料中各对应组分的比例确定。The solvent may include a volatile organic solvent that does not chemically react with the thermosetting polymer monomer. The volatile organic solvent can be selected from but not limited to N-methylpyrrolidone (NMP), methanol, ethanol, ethylene glycol, propanol, isopropanol, acetonitrile, acetone, ether, N,N dimethylformamide One or more of (DMF), N,N dimethylacetamide (DMAc) and tetrahydrofuran (THF). The mass ratio of the silicon particles, the conductive agent, and the thermosetting polymer monomer may be (30-50): (1-20): (4-10), according to each of the silicon negative electrode materials. The proportions of the corresponding components are determined.

在步骤S20中,所述采用喷雾干燥制备所述硅负极材料前体颗粒时,所述硅颗粒、所述导电剂和所述热固性高分子聚合物单体混合形成的分散液通过雾化器雾化成细小的液滴,所述液滴与喷入的热空气充分接触,使得溶剂迅速汽化,从而收集得到球形或类球形的硅负极材料前体颗粒。通过调整所述硅颗粒、所述导电剂以及所述热固性高分子聚合物单体的比例,可以得到三者均匀混合,或者核壳结构的硅负极材料前体颗粒。通过提高喷雾干燥中溶剂挥发速度,可以形成核疏松,壳密实的核壳结构。In step S20, when the silicon anode material precursor particles are prepared by spray drying, the dispersion liquid formed by mixing the silicon particles, the conductive agent and the thermosetting polymer monomer is misted by an atomizer The droplets are formed into fine droplets, and the droplets are fully contacted with the injected hot air, so that the solvent is rapidly vaporized, thereby collecting spherical or quasi-spherical silicon anode material precursor particles. By adjusting the proportions of the silicon particles, the conductive agent and the thermosetting polymer monomer, the three can be uniformly mixed, or the silicon anode material precursor particles with a core-shell structure can be obtained. By increasing the solvent evaporation rate in spray drying, a core-shell structure with loose core and dense shell can be formed.

在一实施例中,所述喷雾干燥的温度可以为50~250℃。所述喷雾干燥的温度可以根据所述热固性高分子聚合物单体和溶剂的种类进行调整。In one embodiment, the temperature of the spray drying may be 50-250°C. The temperature of the spray drying can be adjusted according to the type of the thermosetting polymer monomer and the solvent.

优选的,在所述步骤S10和S20之间,还包括:对所述分散液进行球磨的步骤,通过球磨减小硅颗粒的粒径。所述球磨温度可以为常温。球磨后的所述硅颗粒的粒径可以为10nm~500nm。Preferably, between the steps S10 and S20, the method further includes: a step of ball-milling the dispersion, and reducing the particle size of the silicon particles by ball-milling. The ball milling temperature can be normal temperature. The particle size of the silicon particles after ball milling may be 10 nm˜500 nm.

在喷雾干燥温度太低时,还可以包括步骤S30:将所述硅负极材料前体颗粒进行加热,使所述热固性高分子聚合物单体交联聚合为所述热固性高分子聚合物。步骤S30中,在所述加热条件下,硅负极材料前体颗粒的外层和内部的所述热固性高分子聚合物单体交联形成具有三维网络结构的热固性高分子聚合物。所述加热交联的温度根据热固性高分子聚合物的种类进行调整。在一实施例中,所述热固性高分子聚合物为聚酰亚胺,所述聚酰亚胺加热交联的温度可以为200℃~400℃。可以理解,加热过程并非使聚合物发生热解或碳化形成碳单质,因此需要控制加热温度不致过高,使聚合物单体交联聚合得到具有一定强度和韧性的热固性交联聚合物即可。When the spray drying temperature is too low, step S30 may also be included: heating the silicon anode material precursor particles to cross-link and polymerize the thermosetting polymer monomer into the thermosetting polymer. In step S30, under the heating condition, the outer layer of the silicon anode material precursor particles and the thermosetting polymer monomer inside are cross-linked to form a thermosetting polymer having a three-dimensional network structure. The temperature of the thermal crosslinking is adjusted according to the type of the thermosetting polymer. In one embodiment, the thermosetting polymer is polyimide, and the temperature of the polyimide for crosslinking by heating may be 200°C to 400°C. It can be understood that the heating process does not cause the polymer to be pyrolyzed or carbonized to form a carbon element, so it is necessary to control the heating temperature so as not to be too high, so that the polymer monomer can be cross-linked and polymerized to obtain a thermosetting cross-linked polymer with certain strength and toughness.

本发明实施例还提供一种电化学电池,包括正极、负极及电解质,所述负极包括所述的硅负极材料。An embodiment of the present invention further provides an electrochemical cell, including a positive electrode, a negative electrode and an electrolyte, and the negative electrode includes the silicon negative electrode material.

在一实施例中,所述负极还可以包括负极集流体,所述硅负极材料与易挥发有机溶剂制备成浆料,涂覆在负极集流体表面,真空、保护气体或惰性气体中干燥后得到负极。In one embodiment, the negative electrode may further include a negative electrode current collector, and the silicon negative electrode material and a volatile organic solvent are prepared into a slurry, which is coated on the surface of the negative electrode current collector, and is obtained after drying in vacuum, protective gas or inert gas. negative electrode.

所述易挥发有机溶剂可以选自不能溶解所述硅负极材料,不与所述硅负极材料发生化学反应,且能够在较低温度下完全去除的溶剂,例如低分子量易挥发有机溶剂,可以选自但不限于N-甲基吡咯烷酮(NMP)、甲醇、乙醇、乙二醇、丙醇、异丙醇、乙腈、丙酮、乙醚、N,N二甲基甲酰胺(DMF)、N,N二甲基乙酰胺(DMAc)及四氢呋喃(THF)中的一种或一种以上。The volatile organic solvent can be selected from solvents that cannot dissolve the silicon negative electrode material, do not chemically react with the silicon negative electrode material, and can be completely removed at a lower temperature, such as low molecular weight volatile organic solvents, which can be selected. From but not limited to N-methylpyrrolidone (NMP), methanol, ethanol, ethylene glycol, propanol, isopropanol, acetonitrile, acetone, ether, N,N dimethylformamide (DMF), N,N diethyl ether One or more of methylacetamide (DMAc) and tetrahydrofuran (THF).

所述正极可以包括正极材料及正极集流体,所述正极材料与易挥发有机溶剂制备成浆料,涂覆在正极集流体表面,真空、保护气体或惰性气体中干燥后得到正极。The positive electrode may include a positive electrode material and a positive electrode current collector, the positive electrode material and a volatile organic solvent are prepared into a slurry, coated on the surface of the positive electrode current collector, and dried in vacuum, protective gas or inert gas to obtain the positive electrode.

优选的,所述电化学电池可以为锂离子电池、钠离子电池或镁离子电池。所述正极材料可以包括正极活性材料、导电剂和粘结剂。Preferably, the electrochemical battery may be a lithium-ion battery, a sodium-ion battery or a magnesium-ion battery. The positive electrode material may include a positive electrode active material, a conductive agent, and a binder.

在一实例中,所述电化学电池为锂离子电池,正极活性材料及电解质均含有锂离子。所述正极活性材料可以为锂过渡金属氧化物,如层状结构的锂过渡金属氧化物,尖晶石型结构的锂过渡金属氧化物以及橄榄石型结构的锂过渡金属氧化物中的至少一种,例如,橄榄石型磷酸铁锂、层状结构钴酸锂、层状结构锰酸锂、尖晶石型锰酸锂、锂镍锰氧化物及锂镍钴锰氧化物。In one example, the electrochemical cell is a lithium ion cell, and both the positive electrode active material and the electrolyte contain lithium ions. The positive electrode active material may be a lithium transition metal oxide, such as at least one of a layered lithium transition metal oxide, a spinel-type lithium transition metal oxide, and an olivine-type lithium transition metal oxide. Species, for example, olivine-type lithium iron phosphate, layered-structure lithium cobaltate, layered-structure lithium manganate, spinel-type lithium manganate, lithium nickel manganese oxide, and lithium nickel cobalt manganese oxide.

在另一实施例中,所述电化学电池为钠离子电池,正极活性材料及电解质均含有钠离子。所述正极活性材料可以为钠的层状过渡金属氧化物(如NaxCoO2),隧道结构氧化物(如Na0.44MnO2),聚阴离子型化合物(Na3V2(PO4)3)以及简单化合物(如Na2S)中的至少一种。In another embodiment, the electrochemical cell is a sodium ion battery, and both the positive electrode active material and the electrolyte contain sodium ions. The positive electrode active material can be a layered transition metal oxide of sodium (such as Na x CoO 2 ), a tunnel structure oxide (such as Na 0.44 MnO 2 ), a polyanionic compound (Na 3 V 2 (PO 4 ) 3 ) and at least one of simple compounds such as Na2S.

所述正极与硅负极材料中的导电剂可以分别相同或不同。The conductive agents in the positive electrode material and the silicon negative electrode material may be the same or different, respectively.

所述正极集流体和负极集流体用于分别担载所述正极材料和硅负极材料,并传导电流,形状可以为箔片或网状。所述正极集流体的材料可以选自铝、钛、不锈钢、碳布或碳纸。所述负极集流体的材料可以选自铜、镍、不锈钢、碳布或碳纸。The positive electrode current collector and the negative electrode current collector are used to respectively support the positive electrode material and the silicon negative electrode material, and conduct current, and can be in the shape of a foil or a mesh. The material of the positive electrode current collector can be selected from aluminum, titanium, stainless steel, carbon cloth or carbon paper. The material of the negative electrode current collector can be selected from copper, nickel, stainless steel, carbon cloth or carbon paper.

在一实施例中,所述电化学电池还可以包括设置在正极与负极之间的隔膜,所述电解质为电解液,浸润所述隔膜、正极及负极。在另一实施例中,所述电化学电池的电解质为固态电解质膜或凝胶电解质膜,代替隔膜设置在正极与负极之间。In one embodiment, the electrochemical cell may further include a separator disposed between the positive electrode and the negative electrode, and the electrolyte is an electrolyte that infiltrates the separator, the positive electrode and the negative electrode. In another embodiment, the electrolyte of the electrochemical cell is a solid electrolyte membrane or a gel electrolyte membrane, which is arranged between the positive electrode and the negative electrode instead of the separator.

所述隔膜可以是传统的锂电池隔膜,能够隔绝电子并使金属离子,如锂离子通过。所述隔膜可以为有机聚合物隔膜或者无机隔膜中的任意一种,例如可以选自但不限于聚乙烯多孔膜、聚丙烯多孔膜、聚乙烯-聚丙烯双层多孔膜、聚丙烯-聚乙烯-聚丙烯三层多孔膜、玻璃纤维多孔膜、无纺布多孔膜、电纺丝多孔膜、PVDF-HFP多孔膜及聚丙烯腈多孔膜中的任意一种。所述无纺布隔膜可以列举如聚酰亚胺纳米纤维无纺布、聚对苯二甲酸乙二酯(PET)纳米纤维无纺布、纤维素纳米纤维无纺布、芳纶纳米纤维无纺布、尼龙纳米纤维无纺布及聚偏氟乙烯(PVDF)纳米纤维无纺布。所述电纺丝多孔膜可以列举如聚酰亚胺电纺丝膜、聚对苯二甲酸乙二酯电纺丝膜及聚偏氟乙烯电纺丝膜。The separator may be a conventional lithium battery separator capable of isolating electrons and allowing metal ions, such as lithium ions, to pass through. The separator can be any one of an organic polymer separator or an inorganic separator, for example, it can be selected from but not limited to polyethylene porous membrane, polypropylene porous membrane, polyethylene-polypropylene double-layer porous membrane, polypropylene-polyethylene porous membrane - Any one of polypropylene three-layer porous membrane, glass fiber porous membrane, non-woven porous membrane, electrospun porous membrane, PVDF-HFP porous membrane and polyacrylonitrile porous membrane. The non-woven separator can be listed as polyimide nanofiber nonwoven, polyethylene terephthalate (PET) nanofiber nonwoven, cellulose nanofiber nonwoven, aramid nanofiber nonwoven cloth, nylon nanofiber nonwoven and polyvinylidene fluoride (PVDF) nanofiber nonwoven. The electrospun porous membrane can be exemplified by polyimide electrospun membrane, polyethylene terephthalate electrospun membrane, and polyvinylidene fluoride electrospun membrane.

所述电解液为非水电解液,包括溶剂及溶于所述溶剂的电解质,该溶剂可选自但不限于环状碳酸酯、链状碳酸酯、环状醚类、链状醚类、腈类及酰胺类中的一种或多种,如碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、二乙醚、乙腈、丙腈、苯甲醚、丁酸酯、戊二腈、已二腈、γ-丁内酯、γ-戊内酯、四氢呋喃、1,2-二甲氧基乙烷及乙腈及二甲基甲酰胺中的一种或多种。The electrolyte is a non-aqueous electrolyte, including a solvent and an electrolyte dissolved in the solvent, the solvent can be selected from but not limited to cyclic carbonates, chain carbonates, cyclic ethers, chain ethers, nitriles One or more of amides and amides, such as ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl acetate, propyl acetate, propionic acid Methyl ester, ethyl propionate, diethyl ether, acetonitrile, propionitrile, anisole, butyrate, glutaronitrile, adiponitrile, γ-butyrolactone, γ-valerolactone, tetrahydrofuran, 1,2- One or more of dimethoxyethane, acetonitrile and dimethylformamide.

当所述电化学电池为锂离子电池时,所述电解质为锂盐,可选自但不限于氯化锂(LiCl)、六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、甲磺酸锂(LiCH3SO3)、三氟甲磺酸锂(LiCF3SO3)、六氟砷酸锂(LiAsF6)、高氯酸锂(LiClO4)及双草酸硼酸锂(LiBOB)中的一种或多种。When the electrochemical cell is a lithium ion battery, the electrolyte is a lithium salt, which can be selected from, but not limited to, lithium chloride (LiCl), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), methanesulfonic acid One of lithium (LiCH 3 SO 3 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium perchlorate (LiClO 4 ) and lithium bis-oxalate borate (LiBOB) one or more.

当所述电化学电池为钠离子电池时,所述电解质为钠盐,可选自六氟磷酸钠(NaPF6)、高氯酸钠(NaClO4)、双三氟甲基磺酞亚胺钠(NaTFSI)中的一种或多种,优选为高氯酸钠(NaClO4)。When the electrochemical cell is a sodium-ion battery, the electrolyte is a sodium salt, which can be selected from sodium hexafluorophosphate (NaPF 6 ), sodium perchlorate (NaClO 4 ), sodium bis-trifluoromethylsulfophthalimide One or more of (NaTFSI), preferably sodium perchlorate (NaClO 4 ).

所述电化学电池还可以包括密封壳体,所述正极、负极、隔膜及电解质设置在所述密封壳体中。The electrochemical cell may further include a sealed casing in which the positive electrode, the negative electrode, the separator and the electrolyte are disposed.

实施例1Example 1

将硅颗粒、KS-6和聚酰亚胺单体在乙醇溶液中混合形成分散液。在分散液中,硅颗粒的质量分数为40%,导电剂的质量分数为10%,聚酰亚胺单体的质量分数为5%,其余为乙醇溶剂。The silicon particles, KS-6 and polyimide monomer were mixed in an ethanol solution to form a dispersion. In the dispersion liquid, the mass fraction of silicon particles is 40%, the mass fraction of conductive agent is 10%, the mass fraction of polyimide monomer is 5%, and the rest is ethanol solvent.

将分散液在常温下球磨,至硅颗粒的粒径为500nm以下。The dispersion was ball-milled at room temperature until the particle size of the silicon particles was 500 nm or less.

对球磨后的分散液在100℃~120℃下进行喷雾干燥形成硅负极材料前体颗粒。The ball-milled dispersion is spray-dried at 100° C. to 120° C. to form silicon anode material precursor particles.

将硅负极材料前体颗粒在280℃~320℃进行加热交联,热固性高分子聚合物单体交联为热固性高分子聚合物。得到硅负极材料二次复合颗粒,二次复合颗粒的电子显微镜照片请参阅图2A、图2B所示。The silicon negative electrode material precursor particles are heated and cross-linked at 280° C. to 320° C., and the thermosetting macromolecular polymer monomer is cross-linked to form a thermosetting macromolecular polymer. The secondary composite particles of the silicon negative electrode material are obtained, and the electron microscope photos of the secondary composite particles are shown in FIG. 2A and FIG. 2B .

将得到的二次复合颗粒加入到N-甲基吡咯烷酮(NMP)溶剂中,搅拌4小时后涂覆于铜箔上,在120℃温度下真空干燥10小时后制得负极。The obtained secondary composite particles were added to N-methylpyrrolidone (NMP) solvent, stirred for 4 hours, coated on copper foil, and vacuum-dried at 120° C. for 10 hours to obtain a negative electrode.

将制得的负极组装锂离子电池。The prepared negative electrode was assembled into a lithium ion battery.

请参阅表1所示,采用蓝电充放电仪在0.005~4.3V电压范围内测试锂离子电池的电化学性能。Please refer to Table 1 to test the electrochemical performance of lithium-ion batteries in the voltage range of 0.005 to 4.3V using a blue-electric charge-discharge instrument.

实施例2Example 2

将硅颗粒、C45、羧甲基纤维素钠(CMC)和聚丙烯酸(PAA)在水溶液中混合形成分散液。在分散液中,硅颗粒的质量分数为30%,导电剂的质量分数为10%,CMC和PAA的质量分数均为5%,其余为水溶剂。Silicon particles, C45, sodium carboxymethylcellulose (CMC), and polyacrylic acid (PAA) were mixed in an aqueous solution to form a dispersion. In the dispersion liquid, the mass fraction of silicon particles is 30%, the mass fraction of conductive agent is 10%, the mass fraction of CMC and PAA is 5%, and the rest is water solvent.

将硅颗粒和少量红磷粉末混合,在常温下球磨,至硅颗粒的粒径为500nm以下。Mix silicon particles with a small amount of red phosphorus powder, and ball-mill at room temperature until the particle size of silicon particles is below 500 nm.

对球磨后的分散液在100℃~130℃下进行喷雾干燥形成硅负极材料前体颗粒。The ball-milled dispersion is spray-dried at 100° C. to 130° C. to form silicon anode material precursor particles.

将硅负极材料前体颗粒在140℃~170℃进行加热,CMC和PAA交联,得到硅负极材料二次复合颗粒。The silicon anode material precursor particles are heated at 140° C. to 170° C., and the CMC and the PAA are cross-linked to obtain the silicon anode material secondary composite particles.

将得到的二次复合颗粒与锂电池常用导电剂(例如导电石墨)、粘结剂(例如PVDF)和制浆溶剂(例如N-甲基吡咯烷酮,NMP)混合制浆,在120℃温度下真空干燥10小时后制得负极。The obtained secondary composite particles are mixed with a commonly used conductive agent for lithium batteries (such as conductive graphite), a binder (such as PVDF) and a slurry solvent (such as N-methylpyrrolidone, NMP), and the slurry is vacuumed at a temperature of 120 ° C. The negative electrode was prepared after drying for 10 hours.

将制得的负极组装锂离子电池。The prepared negative electrode was assembled into a lithium ion battery.

请参阅表1所示,采用蓝电充放电仪在0.005~4.3V电压范围内测试锂离子电池的电化学性能。Please refer to Table 1 to test the electrochemical performance of lithium-ion batteries in the voltage range of 0.005 to 4.3V using a blue-electric charge-discharge instrument.

实施例3Example 3

实施例3与实施例1基本相同,区别仅在于聚酰亚胺单体在分散液中的质量分数为2%,硅颗粒的质量分数为37%。Example 3 is basically the same as Example 1, except that the mass fraction of polyimide monomer in the dispersion liquid is 2%, and the mass fraction of silicon particles is 37%.

实施例4Example 4

实施例4与实施例1基本相同,区别仅在于聚酰亚胺单体在分散液中的质量分数为20%,硅颗粒的质量分数为25%。Example 4 is basically the same as Example 1, except that the mass fraction of polyimide monomer in the dispersion liquid is 20%, and the mass fraction of silicon particles is 25%.

对比例1Comparative Example 1

提供实施例1得到的硅负极材料二次复合颗粒,将硅负极材料二次复合颗粒在氮气气氛下进行烧结,得到所述硅碳复合微球。烧结条件为由室温升至烧结温度500℃~1000℃,保持所述烧结温度20h~30h,冷却至室温。The silicon negative electrode material secondary composite particles obtained in Example 1 are provided, and the silicon negative electrode material secondary composite particles are sintered in a nitrogen atmosphere to obtain the silicon carbon composite microspheres. The sintering condition is to increase from room temperature to a sintering temperature of 500°C to 1000°C, maintain the sintering temperature for 20h to 30h, and cool to room temperature.

表1不同实施例中制备硅基负极材料的电化学性能Table 1 Electrochemical properties of silicon-based anode materials prepared in different examples

Figure BDA0002614389520000091
Figure BDA0002614389520000091

Figure BDA0002614389520000101
Figure BDA0002614389520000101

以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.

以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as limiting the scope of the patent of the present invention. It should be noted that, for those skilled in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

1.一种硅负极材料,其特征在于,所述硅负极材料为二次复合颗粒,所述二次复合颗粒包括硅颗粒、导电剂以及热固性高分子聚合物,所述热固性高分子聚合物至少设置在所述二次复合颗粒的外层。1. a silicon negative electrode material, is characterized in that, described silicon negative electrode material is secondary composite particle, and described secondary composite particle comprises silicon particle, conductive agent and thermosetting macromolecular polymer, and described thermosetting macromolecular polymer at least provided on the outer layer of the secondary composite particles. 2.根据权利要求1所述的硅负极材料,其特征在于,所述硅负极材料为核壳结构,所述热固性高分子聚合物在所述核壳结构的壳层均匀连续设置,所述硅颗粒在所述核壳结构的核心内。2 . The silicon negative electrode material according to claim 1 , wherein the silicon negative electrode material has a core-shell structure, the thermosetting high molecular polymer is uniformly and continuously arranged in the shell layer of the core-shell structure, and the silicon The particles are within the core of the core-shell structure. 3.根据权利要求2所述的硅负极材料,其特征在于,所述核壳结构的所述壳层的致密性大于所述核心的致密性。3 . The silicon negative electrode material according to claim 2 , wherein the density of the shell layer of the core-shell structure is greater than the density of the core. 4 . 4.根据权利要求1所述的硅负极材料,其特征在于,所述热固性高分子材料选自羧甲基纤维素钠和聚丙烯酸的交联聚合物、环氧树脂、酚醛树脂、聚氨酯、聚酰胺及聚酰亚胺中的一种或多种。4. The silicon negative electrode material according to claim 1, wherein the thermosetting polymer material is selected from the group consisting of cross-linked polymer of sodium carboxymethyl cellulose and polyacrylic acid, epoxy resin, phenolic resin, polyurethane, polyacrylic acid One or more of amide and polyimide. 5.根据权利要求1所述的硅负极材料,其特征在于,所述导电剂选自活性炭、石墨烯、碳纳米管、科琴黑、Super P、乙炔黑及石墨中的一种或多种。5. silicon negative electrode material according to claim 1, is characterized in that, described conductive agent is selected from one or more in activated carbon, graphene, carbon nanotube, Ketjen black, Super P, acetylene black and graphite . 6.根据权利要求1所述的硅负极材料,其特征在于,所述硅颗粒、所述导电剂以及所述热固性高分子聚合物的质量比为(30~50):(1~20):(4~10)。6 . The silicon negative electrode material according to claim 1 , wherein the mass ratio of the silicon particles, the conductive agent and the thermosetting polymer is (30-50): (1-20): 6 . (4 to 10). 7.根据权利要求1所述的硅负极材料,其特征在于,所述二次复合颗粒的粒径为5μm~100μm。7 . The silicon negative electrode material according to claim 1 , wherein the particle size of the secondary composite particles is 5 μm˜100 μm. 8 . 8.一种根据权利要求1-7任一项所述的硅负极材料的制备方法,包括:8. A preparation method of the silicon negative electrode material according to any one of claims 1-7, comprising: 将所述硅颗粒、所述导电剂和热固性高分子聚合物单体在溶剂中混合形成分散液;mixing the silicon particles, the conductive agent and the thermosetting polymer monomer in a solvent to form a dispersion; 将所述分散液进行喷雾干燥形成硅负极材料前体颗粒。The dispersion liquid is spray-dried to form silicon anode material precursor particles. 9.根据权利要求8所述的硅负极材料的制备方法,其特征在于,所述喷雾干燥的温度为50℃~400℃。9 . The method for preparing a silicon negative electrode material according to claim 8 , wherein the temperature of the spray drying is 50° C.˜400° C. 10 . 10.一种电化学电池,其特征在于,包括正极、负极及电解质,所述负极包括根据权利要求1-7中任一项所述的硅负极材料。10. An electrochemical cell, comprising a positive electrode, a negative electrode and an electrolyte, the negative electrode comprising the silicon negative electrode material according to any one of claims 1-7.
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