WO2019127766A1 - Composite silicon powder embedding aluminum-rich nanoparticles, preparation method for powder, and application thereof - Google Patents

Composite silicon powder embedding aluminum-rich nanoparticles, preparation method for powder, and application thereof Download PDF

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WO2019127766A1
WO2019127766A1 PCT/CN2018/073549 CN2018073549W WO2019127766A1 WO 2019127766 A1 WO2019127766 A1 WO 2019127766A1 CN 2018073549 W CN2018073549 W CN 2018073549W WO 2019127766 A1 WO2019127766 A1 WO 2019127766A1
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aluminum
silicon
silicon powder
composite
powder
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PCT/CN2018/073549
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French (fr)
Chinese (zh)
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王薇
郭凤祥
王瑶
唐建国
刘继宪
黄林军
焦吉庆
王彦欣
李海东
王久兴
沈文飞
李磊
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青岛大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of silicon powder, in particular to a composite silicon powder encapsulating aluminum-rich nanoparticles and a preparation method and application thereof.
  • the traditional lithium battery anode material is mainly graphite.
  • the specific capacity of graphite is small, which makes it difficult for conventional lithium batteries to meet the requirements of large-capacity, low-weight lithium batteries for electric vehicles and mobile electronic devices.
  • Silicon is a new anode material for lithium batteries and is one of the most promising anode materials for lithium batteries.
  • Due to the poor conductivity of the composite silicon powder the volume expansion during the lithiation process is severe, resulting in pulverization, resulting in poor cycle life, which limits its application in the anode material of lithium batteries.
  • the performance of the composite silicon powder is generally improved in the prior art, mainly in the form of composite by nano silicon aggregate, silicon carbon core shell structure or surface conductive coating.
  • the silicon powder particles are modified.
  • Chinese Patent No. CN103985848A discloses a method for preparing nanoporous silicon by using doped silicon particles, which comprises selecting silicon particles with a certain doping concentration, and after washing with hydrofluoric acid, using nitrate, hydrofluoric acid and oxidizing agent.
  • the solution is reacted and ultrasonically assisted, then washed by centrifugation, and finally processed by dilute nitric acid cleaning and the like to prepare three-dimensional nanoporous silicon; the method mainly uses chemical etching to dissolve the doped particles in the doped silicon particles to obtain Three-dimensional nanostructured porous silicon; such nano-silicon aggregates and silicon-carbon core-shell structure particles have a bulk density due to their porous structure, and silicon particles coated with a conductive coating on the surface are also increased by the increase of the conductive layer.
  • the invention provides a composite silicon powder encapsulating aluminum-rich nano particles, a preparation method and application thereof, and solves the problem that the silicon anode material in the prior art has serious volume expansion during the lithiation process and affects the cycle life of the lithium battery.
  • a composite silicon powder encapsulating an aluminum-rich nanoparticle according to the present invention is achieved by the technical solution that the composite silicon powder comprises a silicon particle matrix and an aluminum-rich nanoparticle, and the silicon particle matrix has a size of 0.2-3 ⁇ m.
  • the radius of the aluminum-rich nanoparticle is 3-10 nm; the composite silicon powder is prepared from the following raw materials by weight: industrial aluminum 85.1-99.0%, industrial silicon 0.9-14.8%, and modifier 0.1-0.6 %.
  • the invention relates to a composite silicon powder in which silicon powder is embedded with aluminum powder nanoparticles, wherein the structure is novel, the particle size of the silicon matrix is small, and the embedded structure is aluminum-rich nano particles; compared with the pure silicon powder, the invention
  • the aluminum-rich nanoparticles in the composite silicon powder improve the electrical conductivity, reduce the hardness, relieve the internal stress of the silicon powder, and delay the pulverization of the silicon powder; the presence of the aluminum-rich nanoparticles enables the lithium ion battery to The nanochannel of the electrolyte is formed during the discharge process, which promotes the charge and mass transfer of the lithium ion battery.
  • the initial discharge capacity of the lithium ion battery reaches 3524.1 mAh/g, and the negative electrode material made of the same size silicon powder without the aluminum-rich nanoparticle.
  • the composite silicon powder of the invention has high bulk density, improves the stability of the skeleton structure, and has low raw material price, and is prepared. The process is simple and controllable, and the cost is low.
  • the weight percentage of silicon element and aluminum element in the composite silicon powder is Si 90.0-99.9% and Al 0.1-10.0%, respectively.
  • the composite silicon powder of the present invention is obtained by melting, cooling, setting, chemically etching, standing, washing and drying industrial aluminum, industrial silicon and a modifier. In the process of chemical corrosion, the modifier is corroded and dissolved with part of the aluminum-rich phase, and a small amount of silicon powder is also filtered out during the standing process. Therefore, the obtained composite silicon powder contains only silicon and aluminum. The content of other impurities is very small.
  • the weight percentage of silicon element and aluminum element in the composite silicon powder is Si 90.0-99.9% and Al 0.1-10.0%, respectively.
  • the aluminum-rich nanoparticles in the composite silicon powder of this composition are uniformly distributed and uniform in size, which is favorable for improving the initial discharge capacity and cycle performance of the lithium ion battery.
  • the silicon particle matrix has a size of from 0.3 to 1.2 ⁇ m.
  • the particle size of the composite silicon powder has an important influence on the performance of the lithium ion battery anode material and the lithium ion battery.
  • the crystal grain size silicon particle substrate of the present invention adapts to large stress changes, delays pulverization, and has a high
  • the volumetric energy density, which is used in the anode material of lithium ion batteries, can further improve the performance of lithium ion batteries.
  • the modifying agent is any one or more of Sb, Sr, and Bi.
  • the modifier and industrial silicon are melted, after heat preservation, it will induce agglomeration of neighboring silicon clusters and solute retention of aluminum atoms, promote the formation of aluminum-rich nanoparticles, and change the nucleation and growth path of silicon.
  • the final modifier leads to silicon. Refinement of the particles.
  • the preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention is realized by the following steps: 1) taking industrial aluminum, industrial silicon and a modifier, and spare; 2) industrial aluminum Heating to melting, adding industrial silicon and modifier, mixing evenly, at 570-850 ° C, holding 15-90 min, to obtain aluminum-silicon alloy melt; 3) taking the aluminum-silicon alloy melt obtained in step 2), 0.1- Cooling at a cooling rate of 100 ° C / s to obtain an aluminum-silicon alloy; 4) cutting the aluminum-silicon alloy obtained in step 3) into small pieces, placed in a mineral acid having a mass concentration of 5-10%, chemically corroding 100-120h The corroded aluminum-silicon alloy is obtained; 5) the corroded aluminum-silicon alloy obtained in step 4) is immersed, stirred, precipitated, and allowed to stand for 4-150 h; 6) the upper layer mixture after the step 5) is allowed to stand. The liquid, centrifuged, and dried to obtain a composite silicon powder.
  • the composite silicon powder of the present invention is obtained by melting, cooling, setting, chemical etching, standing, centrifuging and drying industrial silicon, industrial aluminum and a modifier. During the solidification process of the molten aluminum-silicon alloy, most of the silicon forms a silicon-rich phase; after chemical etching, the aluminum-rich phase is dissolved and the modifier is etched away, thereby obtaining a composite silicon powder in which the aluminum powder is embedded in the silicon powder.
  • the preparation method is simple, convenient to operate, easy to control, and easy to realize industrialization.
  • the chemically corrosive inorganic acid of the present invention is dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid or the like, preferably dilute hydrochloric acid, and of course, dilute sulfuric acid or dilute nitric acid.
  • the standing time is 100-150 h.
  • the invention screens the particle size of the composite silicon powder by standing, and the longer the standing time, the smaller the particle size in the composite silicon powder.
  • the soaking is carried out in deionized water and/or absolute ethanol at a soaking temperature of 15-60 °C.
  • the melting of industrial aluminum is carried out in an induction furnace or an electric resistance furnace.
  • the cooling forming in the step 3) is carried out in a graphite crucible or a clay crucible having a diameter of 5 to 50 mm to ensure a cooling rate of 0.1 to 100 ° C/s. Within the scope and, it can be reused and the process cost is low.
  • the application of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention is achieved by the technical solution of preparing the lithium silicon battery anode material.
  • the conductivity is good, the hardness of the silicon powder is lowered, the stability of the skeleton structure is improved, the charge and mass transfer of the lithium battery are promoted, and the first time of the lithium ion battery is improved. Discharge capacity and cycle performance.
  • the composite silicon powder, the conductive agent, and the binder are mixed at a mass ratio of 15:5:3, deionized water is added, stirred uniformly, allowed to stand, dried, and coated on a copper foil. On, a lithium ion battery anode material is obtained.
  • the composite silicon powder of the invention is mixed with a conductive agent such as acetylene black through a binder, coated on a copper foil to form a negative electrode material for a lithium ion battery, and the preparation thereof is convenient, and the lithium ion battery of the obtained lithium ion battery has a high initial discharge capacity. Good cycle performance.
  • the invention has the beneficial effects that the invention is a composite silicon powder in which silicon powder is embedded with aluminum powder nanoparticles, and the structure thereof is novel, the aluminum-rich nano particles are embedded, and the silicon powder is reduced.
  • the hardness of the composite silicon powder is small, the preparation process is simple and controllable, and the cost is low; compared with the pure silicon powder, the composite silicon powder of the invention has good conductivity, low hardness and the presence of aluminum-rich nanoparticles. It relieves the stress inside the silicon powder and delays the pulverization of the silicon powder.
  • the presence of the aluminum-rich nanoparticles makes the lithium ion battery form the nanochannel of the electrolyte during the discharge process, which promotes the charge and mass transfer of the lithium ion battery.
  • the initial discharge capacity of lithium ion battery reaches 3524.1mAh/g, and the cycle performance of lithium ion battery is up to about 50%.
  • the composite silicon powder of the invention has high bulk density and stable skeleton structure. , the use performance is good.
  • the composite silicon powder of the invention has simple preparation method, convenient operation and easy industrialization.
  • Embodiment 1 is a transmission electron micrograph of a composite silicon powder obtained according to Embodiment 1 of the present invention at a magnification of 50,000 times;
  • Figure 2 is a transmission electron micrograph of Figure 1 at 150,000 times magnification
  • FIG. 3 is a transmission electron micrograph of the aluminum-rich nanoparticle inside the composite silicon powder of FIG. 1;
  • FIG. 4 is a transmission electron micrograph of the lattice phase of the aluminum-rich nanoparticle of FIG. 3;
  • Example 5 is a transmission electron microscope energy spectrum of the composite silicon powder obtained in Example 1 of the present invention.
  • FIG. 6 is a graph showing the cycle performance test of the composite silicon powder and the existing silicon powder used in the lithium ion battery according to the embodiment 1 of the present invention.
  • FIG. 7 is a graph showing the cycle performance test of the composite silicon powder obtained by the second embodiment of the present invention and the existing silicon powder in a lithium ion battery;
  • Figure 8 is an enlarged view of a portion A in Figure 7;
  • Figure 10 is an enlarged view of a portion A in Figure 9;
  • a composite silicon powder encapsulating an aluminum-rich nanoparticle according to the present invention has a size of 0.2-3 ⁇ m.
  • the radius of the aluminum-rich nanoparticle is 3-10 nm; the composite silicon powder is prepared from the following raw materials by weight: industrial aluminum 85.1-99.0%, industrial silicon 0.9-14.8%, and modifier 0.5-0.6%.
  • the weight percentage of silicon element and aluminum element in the composite silicon powder is Si 90.0-99.9% and Al 0.1-10.0%, respectively.
  • the weight percentage of the silicon element and the aluminum element in the composite silicon powder is Si 95.0-99.0% and Al 1.0-5.0%, respectively.
  • the silicon particle matrix has a size of 0.3 to 1.2 ⁇ m.
  • the modifier is any one or more of Sb, Sr, Bi.
  • the preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention comprises the following steps:
  • the aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 0.1-100 ° C / s to obtain an aluminum-silicon alloy;
  • the aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a mineral acid having a mass concentration of 5-10%, and chemically etched for 100-120 hours to obtain an etched aluminum-silicon alloy;
  • step 5 taking the corroded aluminum-silicon alloy obtained in step 4), soaking, stirring, and standing for 4-150 h;
  • the rest time is 100-150 h.
  • the soaking is carried out in deionized water and/or absolute ethanol at a soaking temperature of 15-60 °C.
  • the invention relates to an application of embedding an aluminum-rich nanoparticle-containing composite silicon powder for preparing a lithium ion battery anode material.
  • the composite silicon powder, the conductive agent, and the binder are mixed at a mass ratio of 12:5:3, deionized water is added, stirred uniformly, allowed to stand, dried, and coated on a copper foil to obtain lithium ions.
  • Battery anode material Preferably, the composite silicon powder, the conductive agent, and the binder are mixed at a mass ratio of 12:5:3, deionized water is added, stirred uniformly, allowed to stand, dried, and coated on a copper foil to obtain lithium ions. Battery anode material.
  • the preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention comprises the following steps:
  • the aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 0.1 ° C / s in a clay crucible having a diameter of 50 mm to obtain an aluminum-silicon alloy;
  • the aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a dilute sulfuric acid having a mass concentration of 5%, and chemically etched for 100 hours to obtain an aluminum-silicon alloy after corrosion;
  • step 5 taking the corroded aluminum-silicon alloy obtained in step 4), soaking in absolute ethanol, stirring, and standing for 24 hours;
  • the obtained composite silicon powder was placed on a transmission electron microscope of a G2 F20 model produced by FEI Corporation, and the structure thereof was observed. The obtained results are shown in FIG. 1 to FIG. 4, and the present invention can be seen from FIG. 1 to FIG. 4.
  • the obtained composite silicon powder is a structure in which aluminum-rich nano-particles are embedded in the silicon powder, and the silicon-based matrix is interposed with aluminum-rich nanoparticles, and the surface of the silicon particle substrate is smooth, and the size ranges from 0.5 to 1.5 ⁇ m, and a large amount of nanometers are dispersed inside the silicon particles.
  • the particles, the nanoparticles have an average radius of 4 nm. It can be seen from the transmission electron microscopy spectrum of FIG.
  • the composite silicon powder obtained by the present invention mainly contains two elements of silicon and aluminum, wherein the carbon and oxygen elements, oxygen element, are also shown in FIG. It is caused by the absorption of oxygen in the air during the melting and cooling of the silicon powder and aluminum powder, and the carbon element may be an impurity in the test process. Therefore, in the composite silicon powder, silicon, aluminum and oxygen are The weight percentage is Si 88.6%, Al 8.1% and O 3.3%.
  • the preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention comprises the following steps:
  • the aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 100 ° C / s in a graphite crucible having a diameter of 5 mm to obtain an aluminum-silicon alloy;
  • the aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a diluted hydrochloric acid having a mass concentration of 10%, and chemically etched for 120 hours to obtain an etched aluminum-silicon alloy;
  • step 5 taking the corroded aluminum-silicon alloy obtained in step 4), soaking, stirring, and standing for 4 h;
  • the obtained composite silicon powder was observed on a transmission electron microscope according to the method of Example 1.
  • the test results showed that a large amount of nanoparticles were dispersed in the silicon particles in the composite silicon powder, and the size of the silicon particles ranged from 0.5 to 3 ⁇ m.
  • the average radius of the nanoparticles is 3 nm, and the weight percentages of silicon and aluminum are Si 96.5%, Al, respectively. 3.5%.
  • the preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention comprises the following steps:
  • the aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 10 ° C / s in a graphite crucible having a diameter of 10 mm to obtain an aluminum-silicon alloy;
  • the aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a diluted hydrochloric acid having a mass concentration of 8%, and chemically etched for 110 hours to obtain an aluminum-silicon alloy after corrosion;
  • step 5 taking the corroded aluminum-silicon alloy obtained in step 4), soaking, stirring, and standing for 150 h;
  • the obtained composite silicon powder was observed on a transmission electron microscope according to the method of Example 1.
  • the test results showed that a large amount of nanoparticles were dispersed in the silicon particles in the composite silicon powder, and the size of the silicon particles was in the range of 1-3 ⁇ m.
  • the maximum radius of the nanoparticles is 10 nm, wherein the weight percentages of silicon and aluminum are Si 90.0%, Al, respectively. 10.0%.
  • the three composite silicon powders obtained in the first embodiment to the third embodiment of the present invention and the existing commercially available ordinary silicon powder are respectively mixed with acetylene black (conductive agent): CMC (binder) in a ratio of 48 mg: 20 mg: 12 mg.
  • CMC binder
  • 1 mol/L of LiPF6 as a solvent was used as an electrolyte, and a lithium battery was assembled using a Celgard 2325 polypropylene film as a separator.
  • the cycle life of the battery was tested in the range of 0.01-1.5 V using a LAND-CT2001A lithium battery performance tester. As shown in Figure 6 - Figure 10.
  • the optimum specific capacity of the composite silicon powder obtained by the present invention is about 40% higher than that of the ordinary silicon powder particles when the lithium ion battery is operated for 30 cycles; the same specific capacity.
  • the optimal cycle number of the composite silicon powder obtained by the invention is about 50% higher than that of the ordinary silicon powder particles.
  • the invention has the beneficial effects that the invention is a composite silicon powder in which silicon powder is embedded with aluminum powder nanoparticles, and the structure thereof is novel, the particle size of the silicon matrix is small, and the embedded structure is rich.
  • Aluminum nano particles which can be used as a negative electrode material for lithium batteries; compared with pure silicon powder, the aluminum-rich nanoparticles present in the composite silicon powder of the invention improve conductivity, reduce hardness, and alleviate internal silicon powder Stress, delaying the pulverization of silicon powder; the presence of aluminum-rich nanoparticles makes the lithium ion battery form the nanochannel of the electrolyte during the discharge process, which promotes the charge and mass transfer of the lithium ion battery, and the initial discharge of the lithium ion battery The capacity is up to 3524.1 mAh/g, and the cycle performance of the lithium ion battery is optimally improved by about 50% compared with the anode material made of the same size silicon powder without the aluminum-rich nanoparticle; compared with the existing porous doped silicon
  • the composite silicon powder which

Abstract

A composite silicon powder embedding aluminum-rich nanoparticles, comprising a silicon particle substrate and aluminum-rich nanoparticles, the size of the silicon particle substrate being 0.2-3 μm, and the radius of the aluminum-rich nanoparticles being 3-10 nm. The silicon powder is prepared with the following raw materials in terms of weight percentage: industrial aluminum 85.1-99.0%, industrial silicon 0.9-14.8%, and a modifier 0.1-0.6%. Also disclosed is a preparation method for the composite silicon powder, which is produced by means of melting, cooling and curing, chemical corrosion, standing, centrifugation, and drying. Also disclosed is an application of the composite silicon powder. The silicon powder having embedded therein the aluminum-rich nanoparticles is structurally novel, reduces the hardness of the silicon powder, has a small particle size and a simple and controllable preparation process, is inexpensive, applicable as a negative electrode material of a lithium-ion battery, and capable for forming a nanochannel, and increases the initial discharge capacity and cycle performance of the lithium-ion battery.

Description

一种包埋富铝纳米颗粒的复合硅粉及其制备方法和应用Composite silicon powder encapsulating aluminum-rich nano particles and preparation method and application thereof 技术领域Technical field
本发明涉及硅粉的技术领域，特别是指一种包埋富铝纳米颗粒的复合硅粉及其制备方法和应用。The invention relates to the technical field of silicon powder, in particular to a composite silicon powder encapsulating aluminum-rich nanoparticles and a preparation method and application thereof.
背景技术Background technique
传统的锂电池负极材料主要为石墨，然而，石墨的比容量小，导致传统的锂电池难以满足电动汽车和移动电子设备等对大容量、低重量的锂电池的要求。硅是新型的锂电池负极材料，是最有前途的锂电池负极材料之一。但是，由于复合硅粉的导电性差，锂化过程中的体积膨胀严重，导致粉碎化，致使循环寿命差，限制了其在锂电池负极材料中的应用。The traditional lithium battery anode material is mainly graphite. However, the specific capacity of graphite is small, which makes it difficult for conventional lithium batteries to meet the requirements of large-capacity, low-weight lithium batteries for electric vehicles and mobile electronic devices. Silicon is a new anode material for lithium batteries and is one of the most promising anode materials for lithium batteries. However, due to the poor conductivity of the composite silicon powder, the volume expansion during the lithiation process is severe, resulting in pulverization, resulting in poor cycle life, which limits its application in the anode material of lithium batteries.
为了提高复合硅粉在锂电池负极材料中性能，现有技术中通常对复合硅粉的性能进行改进，主要表现在通过纳米硅聚集体、硅碳核壳结构或表面导电涂层等方式对复合硅粉颗粒进行改性。例如：中国专利CN103985848A公开了一种利用掺杂硅颗粒制备纳米多孔硅的方法，该方法包括选用一定掺杂浓度的硅颗粒，氢氟酸清洗后，选用硝酸盐、氢氟酸、氧化剂配制的溶液反应并进行超声辅助，再经离心清洗，最后通过稀硝酸清洗等后处理制备的三维纳米多孔硅；该方法主要是利用化学刻蚀的方法溶解掺杂硅颗粒中的掺杂颗粒从而得到具有三维纳米结构的多孔硅；这种纳米硅聚集体和硅碳核壳结构的颗粒，由于具有多孔结构而导致其体积密度小，表面涂抹导电涂层的硅颗粒也因为导电层的增加而增加了硅颗粒的体积，从而降低其体积密度；这种改进的硅颗粒用于锂电池负极材料时很容易导致其骨架结构不稳定，并且，纳米硅及其复合材料的制备，通常原材料极为昂贵，成本高，不适于工业化生产。In order to improve the performance of composite silicon powder in the negative electrode material of lithium battery, the performance of the composite silicon powder is generally improved in the prior art, mainly in the form of composite by nano silicon aggregate, silicon carbon core shell structure or surface conductive coating. The silicon powder particles are modified. For example, Chinese Patent No. CN103985848A discloses a method for preparing nanoporous silicon by using doped silicon particles, which comprises selecting silicon particles with a certain doping concentration, and after washing with hydrofluoric acid, using nitrate, hydrofluoric acid and oxidizing agent. The solution is reacted and ultrasonically assisted, then washed by centrifugation, and finally processed by dilute nitric acid cleaning and the like to prepare three-dimensional nanoporous silicon; the method mainly uses chemical etching to dissolve the doped particles in the doped silicon particles to obtain Three-dimensional nanostructured porous silicon; such nano-silicon aggregates and silicon-carbon core-shell structure particles have a bulk density due to their porous structure, and silicon particles coated with a conductive coating on the surface are also increased by the increase of the conductive layer. The volume of silicon particles, thereby reducing its bulk density; such improved silicon particles are liable to cause instability of their skeleton structure when used in lithium battery anode materials, and the preparation of nano-silicon and its composite materials is generally extremely expensive and costly. High, not suitable for industrial production.
技术问题technical problem
本发明提出一种包埋富铝纳米颗粒的复合硅粉及其制备方法和应用，解决了现有技术中的硅负极材料在锂化过程中体积膨胀严重而影响锂电池的循环寿命的问题。The invention provides a composite silicon powder encapsulating aluminum-rich nano particles, a preparation method and application thereof, and solves the problem that the silicon anode material in the prior art has serious volume expansion during the lithiation process and affects the cycle life of the lithium battery.
技术解决方案Technical solution
本发明的一种包埋富铝纳米颗粒的复合硅粉，其技术方案是这样实现的：所述复合硅粉包括硅颗粒基体和富铝纳米颗粒，所述硅颗粒基体的尺寸为0.2-3μm，所述富铝纳米颗粒的半径为3-10nm；所述复合硅粉由以下重量百分含量的原料制备而成：工业铝85.1-99.0%、工业硅0.9-14.8%、变质剂0.1-0.6%。A composite silicon powder encapsulating an aluminum-rich nanoparticle according to the present invention is achieved by the technical solution that the composite silicon powder comprises a silicon particle matrix and an aluminum-rich nanoparticle, and the silicon particle matrix has a size of 0.2-3 μm. The radius of the aluminum-rich nanoparticle is 3-10 nm; the composite silicon powder is prepared from the following raw materials by weight: industrial aluminum 85.1-99.0%, industrial silicon 0.9-14.8%, and modifier 0.1-0.6 %.
本发明是一种硅粉内部包埋有铝粉纳米颗粒的复合硅粉，其结构新颖，硅基体的粒径小，包埋结构为富铝纳米颗粒；与纯的硅粉相比，本发明的复合硅粉存在的富铝纳米颗粒，提高了其导电性，降低了其硬度，缓解了硅粉内部的应力，延缓了硅粉的粉碎化；富铝纳米颗粒的存在，使锂离子电池在放电过程中形成了电解液的纳米通道，促进了锂离子电池的电荷与质量传输，锂离子电池的初次放电容量达3524.1mAh/g，与无富铝纳米颗粒的同尺寸硅粉制作的负极材料相比，锂离子电池的循环性能最高提高了约50%；与现有的多孔掺杂硅相比，本发明的复合硅粉体积密度高，提高了骨架结构的稳定性，原材料价格低廉，制备工艺简单可控，成本低。The invention relates to a composite silicon powder in which silicon powder is embedded with aluminum powder nanoparticles, wherein the structure is novel, the particle size of the silicon matrix is small, and the embedded structure is aluminum-rich nano particles; compared with the pure silicon powder, the invention The aluminum-rich nanoparticles in the composite silicon powder improve the electrical conductivity, reduce the hardness, relieve the internal stress of the silicon powder, and delay the pulverization of the silicon powder; the presence of the aluminum-rich nanoparticles enables the lithium ion battery to The nanochannel of the electrolyte is formed during the discharge process, which promotes the charge and mass transfer of the lithium ion battery. The initial discharge capacity of the lithium ion battery reaches 3524.1 mAh/g, and the negative electrode material made of the same size silicon powder without the aluminum-rich nanoparticle. Compared with the existing porous doped silicon, the composite silicon powder of the invention has high bulk density, improves the stability of the skeleton structure, and has low raw material price, and is prepared. The process is simple and controllable, and the cost is low.
作为一种优选的实施方案，所述复合硅粉中硅元素和铝元素的重量百分含量分别为Si 90.0-99.9%和Al 0.1-10.0%。本发明的复合硅粉是由工业铝、工业硅和变质剂经过熔融、冷却定型、化学腐蚀、静置、清洗和干燥后而得到的。在化学腐蚀的过程中，变质剂随着部分富铝相被腐蚀溶解掉，静置的过程中还有少量的硅粉也被过滤掉，因此，所得复合硅粉中仅含有硅和铝两种元素，其它杂质含量很微小。As a preferred embodiment, the weight percentage of silicon element and aluminum element in the composite silicon powder is Si 90.0-99.9% and Al 0.1-10.0%, respectively. The composite silicon powder of the present invention is obtained by melting, cooling, setting, chemically etching, standing, washing and drying industrial aluminum, industrial silicon and a modifier. In the process of chemical corrosion, the modifier is corroded and dissolved with part of the aluminum-rich phase, and a small amount of silicon powder is also filtered out during the standing process. Therefore, the obtained composite silicon powder contains only silicon and aluminum. The content of other impurities is very small.
作为一种优选的实施方案，所述复合硅粉中硅元素和铝元素的重量百分含量分别为Si 90.0-99.9%和Al 0.1-10.0%。这种组成的复合硅粉中的富铝纳米颗粒分布均匀，尺寸较为一致，有利于提高锂离子电池的初次放电容量和循环性能。As a preferred embodiment, the weight percentage of silicon element and aluminum element in the composite silicon powder is Si 90.0-99.9% and Al 0.1-10.0%, respectively. The aluminum-rich nanoparticles in the composite silicon powder of this composition are uniformly distributed and uniform in size, which is favorable for improving the initial discharge capacity and cycle performance of the lithium ion battery.
作为一种优选的实施方案，所述硅颗粒基体的尺寸为0.3-1.2μm。复合硅粉的粒径大小对锂离子电池负极材料及锂离子电池的性能有着重要的影响，本发明这种晶粒尺寸的硅颗粒基体，适应较大应力变化，延缓粉碎化，并具有较高的体积能量密度，用于锂离子电池负极材料中可以进一步提高锂离子电池的性能。As a preferred embodiment, the silicon particle matrix has a size of from 0.3 to 1.2 μm. The particle size of the composite silicon powder has an important influence on the performance of the lithium ion battery anode material and the lithium ion battery. The crystal grain size silicon particle substrate of the present invention adapts to large stress changes, delays pulverization, and has a high The volumetric energy density, which is used in the anode material of lithium ion batteries, can further improve the performance of lithium ion batteries.
作为一种优选的实施方案，所述变质剂为Sb、Sr、Bi中的任意一种或几种。变质剂和工业硅熔融之后，经过保温，会诱导近邻硅原子团簇的团聚并对铝原子进行溶质截留，促进富铝纳米颗粒的形成，并改变硅的形核与生长路径，最终变质剂导致硅颗粒的细化。As a preferred embodiment, the modifying agent is any one or more of Sb, Sr, and Bi. After the modifier and industrial silicon are melted, after heat preservation, it will induce agglomeration of neighboring silicon clusters and solute retention of aluminum atoms, promote the formation of aluminum-rich nanoparticles, and change the nucleation and growth path of silicon. The final modifier leads to silicon. Refinement of the particles.
本发明的一种包埋富铝纳米颗粒的复合硅粉的制备方法，其技术方案是这样实现的：包括以下步骤：1）取工业铝、工业硅和变质剂，备用；2）将工业铝加热至熔化，加入工业硅和变质剂，混合均匀，在570-850℃下，保温15-90min，得铝硅合金熔体；3）将步骤2）所得的铝硅合金熔体，以0.1-100℃/s的冷却速度冷却成型，得铝硅合金；4）将步骤3）所得的铝硅合金切割成小块，置于质量浓度为5-10%的无机酸中，化学腐蚀100-120h，得腐蚀后的铝硅合金；5）取步骤4）所得的腐蚀后的铝硅合金，浸泡，搅拌，沉淀，静置4-150h；6）取步骤5）所得的静置后的上层混合液，离心，干燥，得到复合硅粉。The preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention is realized by the following steps: 1) taking industrial aluminum, industrial silicon and a modifier, and spare; 2) industrial aluminum Heating to melting, adding industrial silicon and modifier, mixing evenly, at 570-850 ° C, holding 15-90 min, to obtain aluminum-silicon alloy melt; 3) taking the aluminum-silicon alloy melt obtained in step 2), 0.1- Cooling at a cooling rate of 100 ° C / s to obtain an aluminum-silicon alloy; 4) cutting the aluminum-silicon alloy obtained in step 3) into small pieces, placed in a mineral acid having a mass concentration of 5-10%, chemically corroding 100-120h The corroded aluminum-silicon alloy is obtained; 5) the corroded aluminum-silicon alloy obtained in step 4) is immersed, stirred, precipitated, and allowed to stand for 4-150 h; 6) the upper layer mixture after the step 5) is allowed to stand. The liquid, centrifuged, and dried to obtain a composite silicon powder.
本发明的复合硅粉是由工业硅、工业铝和变质剂经过熔融、冷却定型、化学腐蚀、静置、离心和干燥后而得到的。熔化的铝硅合金在凝固过程中，绝大部分硅形成富硅相；经过化学腐蚀，将富铝相溶解，并腐蚀掉变质剂，从而得到硅粉内部包埋富铝纳米颗粒的复合硅粉；该制备方法简单，操作方便，容易控制，便于实现产业化。本发明的化学腐蚀的无机酸为稀盐酸、稀硫酸、稀硝酸等，优选为稀盐酸，当然，也可以为稀硫酸或稀硝酸。The composite silicon powder of the present invention is obtained by melting, cooling, setting, chemical etching, standing, centrifuging and drying industrial silicon, industrial aluminum and a modifier. During the solidification process of the molten aluminum-silicon alloy, most of the silicon forms a silicon-rich phase; after chemical etching, the aluminum-rich phase is dissolved and the modifier is etched away, thereby obtaining a composite silicon powder in which the aluminum powder is embedded in the silicon powder. The preparation method is simple, convenient to operate, easy to control, and easy to realize industrialization. The chemically corrosive inorganic acid of the present invention is dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid or the like, preferably dilute hydrochloric acid, and of course, dilute sulfuric acid or dilute nitric acid.
作为一种优选的实施方案，所述步骤5）中，静置时间为100-150h。本发明通过静置对复合硅粉的粒径进行筛选，静置时间越长，复合硅粉中的粒径越小。As a preferred embodiment, in the step 5), the standing time is 100-150 h. The invention screens the particle size of the composite silicon powder by standing, and the longer the standing time, the smaller the particle size in the composite silicon powder.
作为一种优选的实施方案，所述步骤5）中，浸泡是在去离子水和/或无水乙醇中进行，浸泡温度为15-60℃。通常工业铝的熔化是在感应炉或者电阻炉中进行，所述步骤3）中冷却成型是在直径为5-50mm的石墨坩埚或粘土坩埚中进行，以确保冷却速度在0.1-100℃/s范围内，并且，可重复利用，工艺成本低。As a preferred embodiment, in the step 5), the soaking is carried out in deionized water and/or absolute ethanol at a soaking temperature of 15-60 °C. Usually, the melting of industrial aluminum is carried out in an induction furnace or an electric resistance furnace. The cooling forming in the step 3) is carried out in a graphite crucible or a clay crucible having a diameter of 5 to 50 mm to ensure a cooling rate of 0.1 to 100 ° C/s. Within the scope and, it can be reused and the process cost is low.
本发明的一种包埋富铝纳米颗粒的复合硅粉的应用，其技术方案是这样实现的：所述复合硅粉用于制备锂离子电池负极材料。本发明的复合硅粉用于锂离子电池负极材料时，其导电性好，降低了硅粉的硬度，提高骨架结构稳定性，促进了锂电池的电荷与质量传输，提高了锂离子电池的初次放电容量和循环性能。The application of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention is achieved by the technical solution of preparing the lithium silicon battery anode material. When the composite silicon powder of the invention is used for the anode material of the lithium ion battery, the conductivity is good, the hardness of the silicon powder is lowered, the stability of the skeleton structure is improved, the charge and mass transfer of the lithium battery are promoted, and the first time of the lithium ion battery is improved. Discharge capacity and cycle performance.
作为一种优选的实施方案，将所述复合硅粉、导电剂、粘合剂按照质量比为15:5:3混合，添加去离子水，搅拌均匀，静置，干燥，涂覆在铜箔上，得到锂离子电池负极材料。本发明的复合硅粉与导电剂如乙炔黑经过粘合剂混合，涂覆在铜箔上制成锂离子电池负极材料，其制备方便，所得锂离子电池的锂离子电池的初次放电容量高，循环性能好。As a preferred embodiment, the composite silicon powder, the conductive agent, and the binder are mixed at a mass ratio of 15:5:3, deionized water is added, stirred uniformly, allowed to stand, dried, and coated on a copper foil. On, a lithium ion battery anode material is obtained. The composite silicon powder of the invention is mixed with a conductive agent such as acetylene black through a binder, coated on a copper foil to form a negative electrode material for a lithium ion battery, and the preparation thereof is convenient, and the lithium ion battery of the obtained lithium ion battery has a high initial discharge capacity. Good cycle performance.
有益效果Beneficial effect
与现有技术相比，本发明的有益效果是：本发明是一种硅粉内部包埋有铝粉纳米颗粒的复合硅粉，其结构新颖，包埋有富铝纳米颗粒，降低了硅粉的硬度，并且，复合硅粉的粒径小，制备工艺简单可控，成本低；与纯的硅粉相比，本发明的复合硅粉导电性好，硬度较低，富铝纳米颗粒的存在缓解了硅粉内部的应力，延缓了硅粉的粉碎化；富铝纳米颗粒的存在，使锂离子电池在放电过程中形成了电解液的纳米通道，促进了锂离子电池的电荷与质量传输，锂离子电池的初次放电容量达3524.1mAh/g，锂离子电池的循环性能最高提高了约50%；与现有的多孔掺杂硅相比，本发明的复合硅粉体积密度高，骨架结构稳定，使用性能好。本发明的复合硅粉制备方法简单，操作方便，易于实现产业化。Compared with the prior art, the invention has the beneficial effects that the invention is a composite silicon powder in which silicon powder is embedded with aluminum powder nanoparticles, and the structure thereof is novel, the aluminum-rich nano particles are embedded, and the silicon powder is reduced. The hardness of the composite silicon powder is small, the preparation process is simple and controllable, and the cost is low; compared with the pure silicon powder, the composite silicon powder of the invention has good conductivity, low hardness and the presence of aluminum-rich nanoparticles. It relieves the stress inside the silicon powder and delays the pulverization of the silicon powder. The presence of the aluminum-rich nanoparticles makes the lithium ion battery form the nanochannel of the electrolyte during the discharge process, which promotes the charge and mass transfer of the lithium ion battery. The initial discharge capacity of lithium ion battery reaches 3524.1mAh/g, and the cycle performance of lithium ion battery is up to about 50%. Compared with the existing porous doped silicon, the composite silicon powder of the invention has high bulk density and stable skeleton structure. , the use performance is good. The composite silicon powder of the invention has simple preparation method, convenient operation and easy industrialization.
附图说明DRAWINGS
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，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，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 used in the embodiments or the description of the prior art will be briefly described below. Obviously, the drawings in the following description are only It is a certain embodiment of the present invention, and other drawings can be obtained from those skilled in the art without any creative work.
图1为本发明实施例一所得复合硅粉在50000倍放大倍数下的透射电镜图；1 is a transmission electron micrograph of a composite silicon powder obtained according to Embodiment 1 of the present invention at a magnification of 50,000 times;
图2为图1在150000倍放大倍数下的透射电镜图；Figure 2 is a transmission electron micrograph of Figure 1 at 150,000 times magnification;
图3为图1中复合硅粉内部的富铝纳米颗粒的透射电镜图；3 is a transmission electron micrograph of the aluminum-rich nanoparticle inside the composite silicon powder of FIG. 1;
图4为图3中富铝纳米颗粒的晶格相的透射电镜图；4 is a transmission electron micrograph of the lattice phase of the aluminum-rich nanoparticle of FIG. 3;
图5为本发明实施例一所得复合硅粉的透射电镜能谱图；5 is a transmission electron microscope energy spectrum of the composite silicon powder obtained in Example 1 of the present invention;
图6为本发明实施例一所得复合硅粉和现有硅粉分别用于锂离子电池中循环性能测试图；6 is a graph showing the cycle performance test of the composite silicon powder and the existing silicon powder used in the lithium ion battery according to the embodiment 1 of the present invention;
图7为本发明实施例二所得复合硅粉和现有硅粉分别用于锂离子电池中循环性能测试图；7 is a graph showing the cycle performance test of the composite silicon powder obtained by the second embodiment of the present invention and the existing silicon powder in a lithium ion battery;
图8为图7中A处的放大图；Figure 8 is an enlarged view of a portion A in Figure 7;
图9为本发明实施例三所得复合硅粉和现有硅粉分别用于锂离子电池中循环性能测试图；9 is a test chart of the cycle performance of the composite silicon powder obtained by the third embodiment of the present invention and the existing silicon powder in a lithium ion battery;
图10为图9中A处的放大图；Figure 10 is an enlarged view of a portion A in Figure 9;
图中：○-复合硅粉的充电过程；△-普通硅粉的充电过程；■-复合硅粉的放电过程；●-普通硅粉的放电过程。In the figure: ○-charging process of composite silicon powder; △-charging process of ordinary silicon powder; ■-discharging process of composite silicon powder; ●-discharging process of ordinary silicon powder.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are clearly and completely described in the following with reference to the accompanying drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
参阅附图1、附图2、附图3、附图4和附图5，本发明的一种包埋富铝纳米颗粒的复合硅粉，所述硅颗粒基体的尺寸为0.2-3μm，所述富铝纳米颗粒的半径为3-10nm；所述复合硅粉由以下重量百分含量的原料制备而成：工业铝85.1-99.0%、工业硅0.9-14.8%、变质剂0.1-0.6%。Referring to FIG. 1, FIG. 2, FIG. 3, FIG. 4 and FIG. 5, a composite silicon powder encapsulating an aluminum-rich nanoparticle according to the present invention has a size of 0.2-3 μm. The radius of the aluminum-rich nanoparticle is 3-10 nm; the composite silicon powder is prepared from the following raw materials by weight: industrial aluminum 85.1-99.0%, industrial silicon 0.9-14.8%, and modifier 0.5-0.6%.
优选地，所述复合硅粉中硅元素和铝元素的重量百分含量分别为Si 90.0-99.9%和Al 0.1-10.0%。Preferably, the weight percentage of silicon element and aluminum element in the composite silicon powder is Si 90.0-99.9% and Al 0.1-10.0%, respectively.
具体地，所述复合硅粉中硅元素和铝元素的重量百分含量分别为Si 95.0-99.0%和Al 1.0-5.0%。Specifically, the weight percentage of the silicon element and the aluminum element in the composite silicon powder is Si 95.0-99.0% and Al 1.0-5.0%, respectively.
进一步地，所述硅颗粒基体的尺寸为0.3-1.2μm。Further, the silicon particle matrix has a size of 0.3 to 1.2 μm.
更优选地，所述变质剂为Sb、Sr、Bi中的任意一种或几种。More preferably, the modifier is any one or more of Sb, Sr, Bi.
本发明的一种包埋富铝纳米颗粒的复合硅粉的制备方法，包括以下步骤：The preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention comprises the following steps:
1）取工业铝、工业硅和变质剂，备用；1) Take industrial aluminum, industrial silicon and modifiers, and reserve;
2）将工业铝加热至熔化，加入工业硅和变质剂，混合均匀，在570-850℃下，保温15-90min，得铝硅合金熔体；2) heating the industrial aluminum to melt, adding industrial silicon and a modifier, mixing uniformly, and holding at 570-850 ° C for 15 to 90 minutes to obtain an aluminum-silicon alloy melt;
3）将步骤2）所得的铝硅合金熔体，以0.1-100℃/s的冷却速度冷却成型，得铝硅合金； 3) The aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 0.1-100 ° C / s to obtain an aluminum-silicon alloy;
4）将步骤3）所得的铝硅合金切割成小块，置于质量浓度为5-10%的无机酸中，化学腐蚀100-120h，得腐蚀后的铝硅合金；4) The aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a mineral acid having a mass concentration of 5-10%, and chemically etched for 100-120 hours to obtain an etched aluminum-silicon alloy;
5）取步骤4）所得的腐蚀后的铝硅合金，浸泡，搅拌，静置4-150h；5) taking the corroded aluminum-silicon alloy obtained in step 4), soaking, stirring, and standing for 4-150 h;
6）取步骤5）所得的静置后的上层混合液，离心，干燥，得到复合硅粉。6) The supernatant mixture obtained after the step 5) is centrifuged and dried to obtain a composite silicon powder.
优选地，所述步骤5）中，静置时间为100-150h。Preferably, in the step 5), the rest time is 100-150 h.
具体地，所述步骤5）中，浸泡是在去离子水和/或无水乙醇中进行，浸泡温度为15-60℃。Specifically, in the step 5), the soaking is carried out in deionized water and/or absolute ethanol at a soaking temperature of 15-60 °C.
本发明的一种包埋富铝纳米颗粒的复合硅粉的应用，所述复合硅粉用于制备锂离子电池负极材料。The invention relates to an application of embedding an aluminum-rich nanoparticle-containing composite silicon powder for preparing a lithium ion battery anode material.
优选地，将所述复合硅粉、导电剂、粘合剂按照质量比为12:5:3混合，添加去离子水，搅拌均匀，静置，干燥，涂覆在铜箔上，得到锂离子电池负极材料。Preferably, the composite silicon powder, the conductive agent, and the binder are mixed at a mass ratio of 12:5:3, deionized water is added, stirred uniformly, allowed to stand, dried, and coated on a copper foil to obtain lithium ions. Battery anode material.
实施例一Embodiment 1
本发明的一种包埋富铝纳米颗粒的复合硅粉的制备方法，包括以下步骤：The preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention comprises the following steps:
1）按照以下重量百分含量称取原料：工业铝99.0%、工业硅0.9%、变质剂0.6%，备用，其中，变质剂为Sb；1) Weigh the raw materials according to the following weight percentage: industrial aluminum 99.0%, industrial silicon 0.9%, modifier 0.6%, spare, wherein the modifier is Sb;
2）将工业铝置于感应炉中，加热至熔化，加入工业硅和变质剂，混合均匀，在850℃下，保温15min，得铝硅合金熔体；2) The industrial aluminum is placed in an induction furnace, heated to melt, industrial silicon and a modifier are added, uniformly mixed, and incubated at 850 ° C for 15 min to obtain an aluminum-silicon alloy melt;
3）将步骤2）所得的铝硅合金熔体，在直径为50mm的粘土坩埚中以0.1℃/s的冷却速度冷却成型，得铝硅合金；3) The aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 0.1 ° C / s in a clay crucible having a diameter of 50 mm to obtain an aluminum-silicon alloy;
4）将步骤3）所得的铝硅合金切割成小块，置于质量浓度为5%的稀硫酸中，化学腐蚀100h，得腐蚀后的铝硅合金；4) The aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a dilute sulfuric acid having a mass concentration of 5%, and chemically etched for 100 hours to obtain an aluminum-silicon alloy after corrosion;
5）取步骤4）所得的腐蚀后的铝硅合金，在无水乙醇中浸泡，搅拌，静置24h；5) taking the corroded aluminum-silicon alloy obtained in step 4), soaking in absolute ethanol, stirring, and standing for 24 hours;
6）取步骤5）所得的静置后的上层混合液，离心，干燥，得到复合硅粉。6) The supernatant mixture obtained after the step 5) is centrifuged and dried to obtain a composite silicon powder.
将所得复合硅粉置于FEI公司生产的G2 F20型号的透射电子显微镜上观察其结构，所得结果如附图1至附图4所示，由附图1至附图4可以看出，本发明所得复合硅粉是在硅粉内部包埋富铝纳米颗粒的结构，硅基体中间夹杂着富铝纳米颗粒，硅颗粒基体表面光滑，尺寸范围在0.5-1.5μm，硅颗粒内部弥散有大量的纳米颗粒，纳米颗粒的平均半径为4nm。由附图5的透射电镜能谱图上可以看出，本发明所得复合硅粉中主要含有硅和铝两种元素，其中，附图5中还显示出的碳和氧两种元素，氧元素是硅粉和铝粉在熔融、冷却定型过程中吸收空气中氧气而带来的，而碳元素可能是测试过程中的杂质，因此，该复合硅粉中，硅元素、铝元素和氧元素的重量百分含量分别为Si 88.6%、Al 8.1%和O 3.3%。The obtained composite silicon powder was placed on a transmission electron microscope of a G2 F20 model produced by FEI Corporation, and the structure thereof was observed. The obtained results are shown in FIG. 1 to FIG. 4, and the present invention can be seen from FIG. 1 to FIG. The obtained composite silicon powder is a structure in which aluminum-rich nano-particles are embedded in the silicon powder, and the silicon-based matrix is interposed with aluminum-rich nanoparticles, and the surface of the silicon particle substrate is smooth, and the size ranges from 0.5 to 1.5 μm, and a large amount of nanometers are dispersed inside the silicon particles. The particles, the nanoparticles have an average radius of 4 nm. It can be seen from the transmission electron microscopy spectrum of FIG. 5 that the composite silicon powder obtained by the present invention mainly contains two elements of silicon and aluminum, wherein the carbon and oxygen elements, oxygen element, are also shown in FIG. It is caused by the absorption of oxygen in the air during the melting and cooling of the silicon powder and aluminum powder, and the carbon element may be an impurity in the test process. Therefore, in the composite silicon powder, silicon, aluminum and oxygen are The weight percentage is Si 88.6%, Al 8.1% and O 3.3%.
实施例二Embodiment 2
本发明的一种包埋富铝纳米颗粒的复合硅粉的制备方法，包括以下步骤：The preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention comprises the following steps:
1）按照以下重量百分含量称取原料：工业铝85.1%、工业硅14.8%、变质剂0.1%，备用，其中，变质剂为Sr；1) Weigh the raw materials according to the following weight percentage: industrial aluminum 85.1%, industrial silicon 14.8%, modifier 0.1%, spare, wherein the modifier is Sr;
2）将铝粉置于电阻炉中，加热至熔化，加入工业硅和变质剂，混合均匀，在750℃下，保温90min，得铝硅合金熔体；2) The aluminum powder is placed in an electric resistance furnace, heated to melt, industrial silicon and a modifier are added, uniformly mixed, and incubated at 750 ° C for 90 min to obtain an aluminum-silicon alloy melt;
3）将步骤2）所得的铝硅合金熔体，在直径为5mm的石墨坩埚中以100℃/s的冷却速度冷却成型，得铝硅合金； 3) The aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 100 ° C / s in a graphite crucible having a diameter of 5 mm to obtain an aluminum-silicon alloy;
4）将步骤3）所得的铝硅合金切割成小块，置于质量浓度为10%的稀盐酸中，化学腐蚀120h，得腐蚀后的铝硅合金；4) The aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a diluted hydrochloric acid having a mass concentration of 10%, and chemically etched for 120 hours to obtain an etched aluminum-silicon alloy;
5）取步骤4）所得的腐蚀后的铝硅合金，浸泡，搅拌，静置4h；5) taking the corroded aluminum-silicon alloy obtained in step 4), soaking, stirring, and standing for 4 h;
6）取步骤5）所得的静置后的上层混合液，离心，干燥，得到复合硅粉。6) The supernatant mixture obtained after the step 5) is centrifuged and dried to obtain a composite silicon powder.
将所得复合硅粉按照实施例一的方法在透射电子显微镜上观察其结构，测试结果表明：该复合硅粉中在硅颗粒内部弥散有大量的纳米颗粒，硅颗粒的尺寸范围在0.5-3μm，纳米颗粒的平均半径为3nm，其硅元素和铝元素的重量百分含量分别为Si 96.5%、Al 3.5%。The obtained composite silicon powder was observed on a transmission electron microscope according to the method of Example 1. The test results showed that a large amount of nanoparticles were dispersed in the silicon particles in the composite silicon powder, and the size of the silicon particles ranged from 0.5 to 3 μm. The average radius of the nanoparticles is 3 nm, and the weight percentages of silicon and aluminum are Si 96.5%, Al, respectively. 3.5%.
实施例三Embodiment 3
本发明的一种包埋富铝纳米颗粒的复合硅粉的制备方法，包括以下步骤：The preparation method of the composite silicon powder encapsulating the aluminum-rich nano particles of the invention comprises the following steps:
1）按照以下重量百分含量称取原料：工业铝89.85%、工业硅10.0%、变质剂0.15%，备用，其中，变质剂为Bi；1) Weigh the raw materials according to the following weight percentage: industrial aluminum 89.85%, industrial silicon 10.0%, modifier 0.55%, spare, wherein the modifier is Bi;
2）将铝粉置于感应炉中，加热至熔化，加入工业硅和变质剂，混合均匀，在570℃下，保温40min，得铝硅合金熔体；2) The aluminum powder is placed in an induction furnace, heated to melt, industrial silicon and a modifier are added, uniformly mixed, and incubated at 570 ° C for 40 min to obtain an aluminum-silicon alloy melt;
3）将步骤2）所得的铝硅合金熔体，在直径为10mm的石墨坩埚中以10℃/s的冷却速度冷却成型，得铝硅合金；3) The aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 10 ° C / s in a graphite crucible having a diameter of 10 mm to obtain an aluminum-silicon alloy;
4）将步骤3）所得的铝硅合金切割成小块，置于质量浓度为8%的稀盐酸中，化学腐蚀110h，得腐蚀后的铝硅合金；4) The aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a diluted hydrochloric acid having a mass concentration of 8%, and chemically etched for 110 hours to obtain an aluminum-silicon alloy after corrosion;
5）取步骤4）所得的腐蚀后的铝硅合金，浸泡，搅拌，静置150h；5) taking the corroded aluminum-silicon alloy obtained in step 4), soaking, stirring, and standing for 150 h;
6）取步骤5）所得的静置后的上层混合液，离心，干燥，得到复合硅粉。6) The supernatant mixture obtained after the step 5) is centrifuged and dried to obtain a composite silicon powder.
将所得复合硅粉按照实施例一的方法在透射电子显微镜上观察其结构，测试结果表明：该复合硅粉中在硅颗粒内部弥散有大量的纳米颗粒，硅颗粒的尺寸范围在1-3μm，纳米颗粒的最大半径为10nm，其中，硅元素和铝元素的重量百分含量分别为Si 90.0%、Al 10.0%。The obtained composite silicon powder was observed on a transmission electron microscope according to the method of Example 1. The test results showed that a large amount of nanoparticles were dispersed in the silicon particles in the composite silicon powder, and the size of the silicon particles was in the range of 1-3 μm. The maximum radius of the nanoparticles is 10 nm, wherein the weight percentages of silicon and aluminum are Si 90.0%, Al, respectively. 10.0%.
将本发明实施例一至实施例三所得的三种复合硅粉以及现有的市售普通硅粉分别与乙炔黑（导电剂）：CMC（粘合剂）按照48mg:20mg:12mg的比例混合，添加去离子水，搅拌均匀，静置，干燥12小时，涂敷在铜箔上，并在手套箱内组装成电池，以体积比为1：1的碳酸亚乙酯/碳酸二乙酯混合液作为溶剂的1mol/L的LiPF6为电解质，以Celgard 2325聚丙烯膜作为隔膜组装锂电池，使用LAND-CT2001A锂电池性能测试仪，在0.01-1.5V范围内进行电池的循环寿命的测试，测试结果如附图6-附图10所示。The three composite silicon powders obtained in the first embodiment to the third embodiment of the present invention and the existing commercially available ordinary silicon powder are respectively mixed with acetylene black (conductive agent): CMC (binder) in a ratio of 48 mg: 20 mg: 12 mg. Add deionized water, stir evenly, let stand, dry for 12 hours, apply on copper foil, and assemble into a battery in a glove box to make a mixture of ethylene carbonate/diethyl carbonate in a volume ratio of 1:1. 1 mol/L of LiPF6 as a solvent was used as an electrolyte, and a lithium battery was assembled using a Celgard 2325 polypropylene film as a separator. The cycle life of the battery was tested in the range of 0.01-1.5 V using a LAND-CT2001A lithium battery performance tester. As shown in Figure 6 - Figure 10.
由附图6至附图10可以看出，该锂离子电池在运行30个循环时，本发明所得复合硅粉的最优比容量比普通硅粉颗粒的比容量高约40%；相同比容量条件下，本发明所得复合硅粉的最优循环次数比普通硅粉颗粒的循环次数高约50%。It can be seen from FIG. 6 to FIG. 10 that the optimum specific capacity of the composite silicon powder obtained by the present invention is about 40% higher than that of the ordinary silicon powder particles when the lithium ion battery is operated for 30 cycles; the same specific capacity. Under the condition, the optimal cycle number of the composite silicon powder obtained by the invention is about 50% higher than that of the ordinary silicon powder particles.
与现有技术相比，本发明的有益效果是：本发明是一种硅粉内部包埋有铝粉纳米颗粒的复合硅粉，其结构新颖，硅基体的粒径小，包埋结构为富铝纳米颗粒，可用于锂电池的负极材料；与纯的硅粉相比，本发明的复合硅粉存在的富铝纳米颗粒，提高了其导电性，降低了其硬度，缓解了硅粉内部的应力，延缓了硅粉的粉碎化；富铝纳米颗粒的存在，使锂离子电池在放电过程中形成了电解液的纳米通道，促进了锂离子电池的电荷与质量传输，锂离子电池的初次放电容量最高达3524.1mAh/g，与无富铝纳米颗粒的同尺寸硅粉制作的负极材料相比，锂离子电池的循环性能最优提高了约50%；与现有的多孔掺杂硅相比，本发明的复合硅粉体积密度高，提高了骨架结构的稳定性，原材料价格低廉，制备工艺简单可控，成本低，易于实现产业化。Compared with the prior art, the invention has the beneficial effects that the invention is a composite silicon powder in which silicon powder is embedded with aluminum powder nanoparticles, and the structure thereof is novel, the particle size of the silicon matrix is small, and the embedded structure is rich. Aluminum nano particles, which can be used as a negative electrode material for lithium batteries; compared with pure silicon powder, the aluminum-rich nanoparticles present in the composite silicon powder of the invention improve conductivity, reduce hardness, and alleviate internal silicon powder Stress, delaying the pulverization of silicon powder; the presence of aluminum-rich nanoparticles makes the lithium ion battery form the nanochannel of the electrolyte during the discharge process, which promotes the charge and mass transfer of the lithium ion battery, and the initial discharge of the lithium ion battery The capacity is up to 3524.1 mAh/g, and the cycle performance of the lithium ion battery is optimally improved by about 50% compared with the anode material made of the same size silicon powder without the aluminum-rich nanoparticle; compared with the existing porous doped silicon The composite silicon powder of the invention has high bulk density, improves the stability of the skeleton structure, has low raw material price, simple and controllable preparation process, low cost and easy industrialization.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., which are included in the spirit and scope of the present invention, should be included in the present invention. Within the scope of protection.

Claims (10)

  1. 一种包埋富铝纳米颗粒的复合硅粉，其特征在于：所述复合硅粉包括硅颗粒基体和富铝纳米颗粒，所述硅颗粒基体的尺寸为0.2-3μm，所述富铝纳米颗粒的半径为3-10nm；A composite silicon powder encapsulating an aluminum-rich nanoparticle, characterized in that the composite silicon powder comprises a silicon particle matrix and an aluminum-rich nanoparticle, the silicon particle matrix having a size of 0.2-3 μm, the aluminum-rich nanoparticle The radius is 3-10 nm;
    所述复合硅粉由以下重量百分含量的原料制备而成：工业铝85.1-99.0%、工业硅0.9-14.8%、变质剂0.1-0.6%。The composite silicon powder is prepared from the following raw materials by weight: 85.1-99.0% of industrial aluminum, 0.9-14.8% of industrial silicon, and 0.1-0.6% of modifier.
  2. 根据权利要求1所述的包埋富铝纳米颗粒的复合硅粉，其特征在于：The composite silicon powder encapsulating an aluminum-rich nanoparticle according to claim 1, wherein:
    所述复合硅粉中硅元素和铝元素的重量百分含量分别为Si 85.0-99.9%和Al 0.1-15.0%。The weight percentage of silicon element and aluminum element in the composite silicon powder is Si 85.0-99.9% and Al 0.1-15.0%, respectively.
  3. 根据权利要求2所述的包埋富铝纳米颗粒的复合硅粉，其特征在于：The composite aluminum powder encapsulating an aluminum-rich nanoparticle according to claim 2, wherein:
    所述复合硅粉中硅元素和铝元素的重量百分含量分别为Si 90.0-99.9%和Al 0.1-10.0%。The weight percentage of silicon element and aluminum element in the composite silicon powder is Si 90.0-99.9% and Al 0.1-10.0%, respectively.
  4. 根据权利要求1所述的包埋富铝纳米颗粒的复合硅粉，其特征在于：The composite silicon powder encapsulating an aluminum-rich nanoparticle according to claim 1, wherein:
    所述硅颗粒基体的尺寸为0.3-1.2μm。The silicon particle matrix has a size of 0.3 to 1.2 μm.
  5. 根据权利要求1所述的包埋富铝纳米颗粒的复合硅粉，其特征在于：The composite silicon powder encapsulating an aluminum-rich nanoparticle according to claim 1, wherein:
    所述变质剂为Sb、Sr、Bi中的任意一种或几种。The modifier is any one or more of Sb, Sr, and Bi.
  6. 根据权利要求1-5中任意一项所述的包埋富铝纳米颗粒的复合硅粉的制备方法，其特征在于：包括以下步骤：The method for preparing an aluminum-rich nanoparticle-compound composite silicon powder according to any one of claims 1 to 5, comprising the steps of:
    1）取工业铝、工业硅和变质剂，备用；1) Take industrial aluminum, industrial silicon and modifiers, and reserve;
    2）将工业铝加热至熔化，加入工业硅和变质剂，混合均匀，在570-850℃下，保温15-90min，得铝硅合金熔体；2) heating the industrial aluminum to melt, adding industrial silicon and a modifier, mixing uniformly, and holding at 570-850 ° C for 15 to 90 minutes to obtain an aluminum-silicon alloy melt;
    3）将步骤2）所得的铝硅合金熔体，以0.1-100℃/s的冷却速度冷却成型，得铝硅合金；3) The aluminum-silicon alloy melt obtained in the step 2) is cooled and formed at a cooling rate of 0.1-100 ° C / s to obtain an aluminum-silicon alloy;
    4）将步骤3）所得的铝硅合金切割成小块，置于质量浓度为5-10%的无机酸中，化学腐蚀100-120h，得腐蚀后的铝硅合金；4) The aluminum-silicon alloy obtained in the step 3) is cut into small pieces, placed in a mineral acid having a mass concentration of 5-10%, and chemically etched for 100-120 hours to obtain an etched aluminum-silicon alloy;
    5）取步骤4）所得的腐蚀后的铝硅合金，浸泡，搅拌，静置4-150h；5) taking the corroded aluminum-silicon alloy obtained in step 4), soaking, stirring, and standing for 4-150 h;
    6）取步骤5）所得的静置后的上层混合液，离心，干燥，得到复合硅粉。6) The supernatant mixture obtained after the step 5) is centrifuged and dried to obtain a composite silicon powder.
  7. 根据权利要求6所述的包埋富铝纳米颗粒的复合硅粉的制备方法，其特征在于：The method for preparing an aluminum-rich nanoparticle-compound composite silicon powder according to claim 6, wherein:
    所述步骤5）中，静置时间为100-150h。In the step 5), the rest time is 100-150 h.
  8. 根据权利要求6所述的包埋富铝纳米颗粒的复合硅粉的制备方法，其特征在于：The method for preparing an aluminum-rich nanoparticle-compound composite silicon powder according to claim 6, wherein:
    所述步骤5）中，浸泡是在去离子水和/或无水乙醇中进行，浸泡温度为15-60℃。In the step 5), the soaking is carried out in deionized water and/or absolute ethanol at a soaking temperature of 15-60 °C.
  9. 根据权利要求1-5中任意一项所述的包埋富铝纳米颗粒的复合硅粉的应用，其特征在于：The use of the composite aluminum powder encapsulating an aluminum-rich nanoparticle according to any one of claims 1 to 5, characterized in that:
    所述复合硅粉用于制备锂离子电池负极材料。The composite silicon powder is used to prepare a lithium ion battery anode material.
  10. 根据权利要求9所述的包埋富铝纳米颗粒的复合硅粉的应用，其特征在于：The invention of embedding an aluminum-rich nanoparticle-containing composite silicon powder according to claim 9, wherein:
    将所述复合硅粉、导电剂、粘合剂按照质量比为12:5:3混合，添加去离子水，搅拌均匀，静置，干燥，涂覆在铜箔上，得到锂离子电池负极材料。The composite silicon powder, the conductive agent and the binder are mixed according to a mass ratio of 12:5:3, deionized water is added, stirred uniformly, allowed to stand, dried, and coated on a copper foil to obtain a lithium ion battery anode material. .
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