CN104617278A - Nano silicon metal composite material and preparation method thereof - Google Patents

Nano silicon metal composite material and preparation method thereof Download PDF

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CN104617278A
CN104617278A CN201310538238.5A CN201310538238A CN104617278A CN 104617278 A CN104617278 A CN 104617278A CN 201310538238 A CN201310538238 A CN 201310538238A CN 104617278 A CN104617278 A CN 104617278A
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silicon
metal
composite material
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metal composite
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CN104617278B (en
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杨娟玉
于冰
卢世刚
王晗
王宁
方升
闫坤
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China Automotive Battery Research Institute Co Ltd
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Beijing General Research Institute for Non Ferrous Metals
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
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    • 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

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Abstract

A nano silicon metal composite used for a negative electrode of a lithium ion battery comprises the following parts: (a) the first component part is simple substance silicon with the content accounting for 5-75mol% of the nano silicon metal composite; (b) the second component part contains a metal element, a compound formed and a silicon oxygen compound formed by the metal element and silicon, the second component part content accounts for 25 to 95mol% of the nano silicon metal composite; and (c) the third component part is simple substance carbon with the content accounting for 0-70mol% of the nano silicon metal composite. The preparation method is as follows: a porous block, comprising silica and metal or metal oxide and the like, and a conductive negative electrode current collector are compounded as a negative electrode, graphite or an inert positive electrode is used as a positive electrode, the negative electrode and the positive electrode are placed in a mixed salt melt electrolyte using CaCl2 or CaCl2 as the main components, voltage is applied between the negative electrode and the positive electrode, current density and electrolytic quantity are controlled, silica in the porous block is electrolyzed and reduced into nano silicon, and a nano silicon metal composite material is prepared on the negative electrode.

Description

Nano silicon metal composite material and preparation method thereof
Technical Field
The invention relates to a silicon metal composite material for a lithium ion battery and a preparation method thereof.
Background
Lithium ion secondary batteries are widely used in various electronic devices. As the demand for and performance of electronic devices for their power system-chemical power source-grows dramatically, most commercial lithium ion batteries have anodes comprising materials such as graphite that incorporate lithium via an intercalation mechanism upon charging. Such an insertion-type anode exhibits better cycle life and coulombic efficiency, but is limited by a lower theoretical capacity (372 mAh/g) and it is difficult to improve the performance of the battery through a battery preparation process.
The second anode material such as Si, Sn and Sb, which introduces lithium through an alloying mechanism during charging, is a better choice of high-capacity anode materials, wherein silicon has the advantages of more than 10 times of theoretical electrochemical capacity (4200 mAh/g) compared with widely used carbon materials, low lithium intercalation voltage (lower than 0.5V), no co-intercalation of solvent molecules in the intercalation process, abundant content in earth crust and the like. However, the silicon material as an anode shows relatively poor cycle life and coulombic efficiency, and the main reasons are that the silicon material has poor conductivity, and the generated internal stress causes the damage of the material structure in the severe volume effect (volume change rate: 280% -310%) generated in the electrochemical lithium-releasing process, so that the separation of electrode materials, electrode materials and conductive agents (such as carbon), adhesives and electrode materials and current collectors is caused, and further the electrical contact is lost, and the cycle performance of the electrode is reduced rapidly.
There are two main solutions proposed to solve this problem: one of the methods is to make silicon into a nano-scale. Because the volume change of silicon can be reduced to some extent with the reduction of particles, the internal stress of the electrode is reduced. However, the nano material is easy to agglomerate in the circulation process, which is not enough to improve the performance of the battery to be practical. Secondly, the method adopts the compounding of materials such as silicon and metal, namely the compounding of nano silicon with electrochemical activity and metal materials with good conductivity. On one hand, the metal material can improve the conductivity of the silicon material, so that all silicon plays a role of an active material in electrochemical lithium desorption, and on the other hand, the metal material can be used as a buffer framework to disperse and buffer internal stress generated by volume change of the silicon material in the lithium desorption process, so that the silicon metal composite material has good cycle performance.
Wang G.X. et al (J.Power. sources, 2000, 88: 278-. Kangkibum et al (chem.Sci., 2011, 2: 1090) grow a silicon-nickel nanowire array on a nickel substrate, silicon is deposited on the outer layer through a vapor deposition method and used for a lithium ion battery cathode material, the inner layer silicon-nickel nanowire is used as a framework, the outer layer silicon is used as an active material, the volume effect of the silicon material in the lithium desorption and intercalation process is inhibited to a certain extent, meanwhile, the conductivity of the silicon material is improved, and the better cycle performance is kept. Zhang Shichao et al (adv. Mater.2010, 22: 5378-. These studies indicate that nano silicon metal composites are generally formed by compounding metal and silicon or silicon alloy and silicon, and the silicon metal can be physically or chemically bonded. The physical combination does not help greatly to improve the cycle performance of the silicon material, and preferably, the silicon and the metal form chemical combination, so that the volume effect of the silicon material can be effectively improved, and the material with stable cycle performance is obtained. The main methods for preparing the silicon metal composite materials at present comprise a chemical vapor deposition method, a thermal vapor deposition method, a high-energy ball milling method and the like. These methods of preparation involve complicated processes (e.g., templating), difficult control of the processes, expensive equipment (e.g., chemical vapor deposition), and difficult mass production.
Disclosure of Invention
The invention aims to overcome the defect that the cycle stability of the existing nano silicon metal composite material is poor due to the separation of silicon and metal in the process of lithium intercalation and deintercalation when the silicon and the metal are used as a negative electrode material of a lithium ion battery because of physical combination, and provides the nano silicon metal composite material with good cycle stability. A small amount of silicon metal alloy can limit the volume change of the nano silicon metal composite material in the process of lithium intercalation and deintercalation, so that silicon and metal in the nano silicon metal composite material can not be separated from each other due to the increase of cycle times, and the cycle stability of the nano silicon metal composite material is improved. The invention also provides a preparation method of the nano silicon metal composite material, which has the advantages of short production flow, no pollution, simple operation, easily obtained raw materials, cheap equipment and easy continuous production.
The invention adopts the following technical scheme:
the invention provides a nano silicon metal composite material for a lithium ion battery, which at least contains simple substance silicon, a second component part which comprises transition metal elements, elements such as aluminum, tin, antimony and the like, alkaline earth elements, carbon and oxygen elements, and the mol percentage of each component is as follows: 5-75 mol% of simple substance silicon, 25-95 mol% of a second component, wherein the second component comprises transition metal, or a combination thereof, or an intermetallic compound formed by the transition metal and the silicon, aluminum, tin, antimony, or a combination thereof, or an intermetallic compound formed by the transition metal and the silicon, alkaline earth metal, carbon, oxygen, or a compound element of the carbon, the oxygen and the silicon, and 0-70 mol% of simple substance carbon. Wherein the molar percentage of the simple substance silicon is further preferably 10-55 mol%. In addition, the material can also contain a silicon oxide compound SiOxX is more than 0 and less than or equal to 2, and the mol percentage of the SiO is 0.1-5 mol percentx. The mole percentage is relative to the nano silicon metal composite material for the lithium ion battery.
The simple substance silicon in the nano silicon metal composite material for the lithium ion battery is one or more of linear, granular, tubular and flaky; the metal is one or more of spherical, quasi-spherical, linear, flaky and reticular; the simple substance carbon is one or more of spherical shape, similar spherical shape, sheet shape, linear shape and tubular shape. Wherein the simple substance silicon is at least one of a nano silicon wire, a nano silicon particle, a nano silicon tube or a nano silicon chip. The particle size of the granular simple substance silicon is less than 100nm, the diameter of the linear simple substance silicon is less than 100nm, the diameter of the tubular simple substance silicon is less than 100nm, and the thickness of the flaky simple substance silicon is less than 100 nm.
The invention provides a preparation method of a nano silicon metal composite material, which comprises the following specific steps: the porous block composed of silicon dioxide and metal material is compounded with conductive cathode current collector to be used as cathode, graphite or inert anode is used as anode, and placed in CaCl2Or with CaCl2In a predominantly mixed salt melt electrolyte, applied between the cathode and the anodeAnd (3) controlling the electrolysis time to ensure that the silicon dioxide in the porous block is electrolyzed and reduced into the nano silicon, and preparing the nano silicon metal composite material at the cathode.
The particle size of the silicon dioxide is 10nm to 1 mu m.
The porous block body composed of the silicon dioxide and the metal is prepared by firstly preparing silicon dioxide powder into a silicon dioxide colloid, wherein the mass ratio of the silicon dioxide to water is 20-50 wt% and 50-80 wt% when the colloid is prepared. Adding metal into a silicon dioxide colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on the metal to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block with the mechanical pressure of 10-200 MPa and the temperature of 800-1400 ℃, wherein the porosity of the obtained porous block is 1-40% by volume, the porosity of the porous block is further preferably 10-30% by volume, and the density is 0.5-2.0 g/cm3Resistivity of 0.1-2. omega. cm
The porous block body composed of the silicon dioxide and the metal oxide is prepared by firstly preparing silicon dioxide powder into a silicon dioxide colloid, adding the metal oxide into the silicon dioxide colloid, carrying out high-speed mechanical fusion to enable the silicon dioxide to be uniformly coated on the metal oxide to form a mixture, then preparing the mixture into a block green body, forming the porous block body by the block green body at a certain mechanical pressure or a certain temperature, preparing the porous block body at a mechanical pressure of 10-200 MPa, preparing the porous block body at a temperature of 800-1400 ℃, wherein the porosity of the obtained porous block body is 1-40 volume percent, and the porosity of the porous block body is further preferably 10-30 volume percent.
The porous block body composed of the silicon dioxide, the metal and the carbon is characterized in that silicon dioxide powder is firstly prepared into a silicon dioxide colloid, the carbon and the metal are added into the silicon dioxide colloid, high-speed mechanical fusion is carried out, the silicon dioxide is uniformly coated on the metal and the carbon to form a mixture, then the mixture is prepared into a block body green body, the block body green body forms the porous block body under a certain mechanical pressure or a certain temperature, the porous block body is prepared into the porous block body under the mechanical pressure of 10-200 MPa, the porous block body is prepared into the temperature of 800-1400 ℃, the porosity of the obtained porous block body is 1-40%, and the porosity of the porous block body is further preferably 10-30.
The porous block body composed of silicon dioxide, metal oxide and carbon is characterized in that silicon dioxide powder is firstly prepared into silicon dioxide colloid, carbon and the metal oxide are added into the silicon dioxide colloid, high-speed mechanical fusion is carried out, so that the silicon dioxide is uniformly coated on the metal oxide and the carbon to form a mixture, then the mixture is prepared into a block body green body, the block body green body forms the porous block body under a certain mechanical pressure or a certain temperature, the porous block body is prepared into the porous block body with the mechanical pressure of 10-200 MPa and the porous block body preparation temperature of 800-1400 ℃, the porosity of the obtained porous block body is 1-40 volume percent, and the porosity of the porous block body is further preferably 10-30 volume percent.
The catalyst is prepared from CaCl2The main mixed salt melt electrolyte is CaCl2+MY1Wherein M is Ba, Li, Al, Cs, Na, K, Mg, Rb, Be or Sr, Y1Is Cl or F.
The voltage is lower than the theoretical decomposition voltage of the electrolyte, and the electrolysis time is equal to or more than the electric quantity required by the theory when the electrolysis electric quantity reaches. The theoretical decomposition voltage is the theoretical calculated decomposition voltage of SiO2 in molten salt, which varies with molten salt composition and temperature. The theoretically required electric quantity is the electric quantity calculated according to the electrons consumed by SiO2 to become simple substance Si, and the electric quantity changes along with the change of the content of SiO 2.
The electrolysis is carried out at a temperature of 500 ℃ and 1000 ℃.
The invention provides a lithium ion battery which comprises a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the negative electrode comprises the nano silicon metal composite material.
The invention has the following characteristics:
(1) the silicon metal ratio in the nano silicon metal composite material can be adjusted by adjusting the ratio of the raw material silicon dioxide and the metal, and the lithium insertion capacity, namely the specific capacity, of the nano silicon metal composite material can be adjusted;
(2) the content of silicon alloy and silicon oxide in the electrolytic product nano silicon metal composite material can be adjusted by controlling the electrolytic electric quantity, and the metallurgical bonding degree between silicon and metal is controlled, so that the electrochemical cycle stability of the nano silicon metal composite material is improved;
(3) the used raw materials have rich sources and low prices, and the raw materials and the preparation process have no pollution to the environment;
(4) the process is simple, the operation is simple and convenient, and the equipment is simple;
(5) the raw materials and the products are added or removed in a solid form, and the continuous production is easy to realize.
Drawings
FIG. 1 is a scanning electron microscope image of example 1, which uses a mixture of nickel powder, nickel protoxide and silicon dioxide as raw materials to prepare a nano silicon-based metal composite material at 900 ℃.
FIG. 2 is a scanning electron microscope image of the silicon-based metal carbon nanowire composite material prepared by the present invention at 950 ℃ in example 16 using a mixture of spherical carbon, nickel powder, nickel protoxide and silica as raw materials.
FIG. 3 is the X-ray diffraction pattern of the nano-silicon metal composite prepared by the invention at 900 ℃ in example 2.
Detailed Description
The invention will be further described with reference to the figures and examples. The description is intended to be illustrative of the invention and is not to be construed as limiting the invention.
The invention provides a nano silicon metal composite material for a lithium ion battery, which at least contains simple substance silicon and metal. The simple substance silicon in the material is obtained by electrolyzing silicon dioxide in raw materials through molten salt by an electrochemical method, the metal is obtained by metal in the raw materials and electrolyzing metal oxide, and the simple substance carbon is obtained by simple substance carbon in the raw materials. Therefore, the ratio of the simple substance silicon to the metal or the carbon in the nano silicon metal composite material can be adjusted by adjusting the ratio of the silicon dioxide, the metal and the metal oxide to the carbon in the raw materials. The lithium intercalation capacity of the nano silicon metal composite material can be adjusted by adjusting the proportion of the simple substance silicon, the metal and the carbon in the material. The silicon content is too low, the specific capacity of the nano silicon metal composite material is too low, and the requirement of the battery can not be met. The ratio of silicon is too high, and under the same other conditions, the specific capacity of the nano silicon metal composite material is higher, but the volume change of silicon caused by lithium intercalation and deintercalation is more severe because partial simple substance silicon cannot form effective combination with metal, so that the cycle performance of a battery using the nano silicon metal composite material is poorer. Thus, the nano-silicon metal composite has a molar percentage of elemental silicon of at least 10%, at least 15%, or at least 20%; the mole percent of elemental silicon may also be up to 35%, up to 40%, up to 45%, up to 50%, or up to 55%. For example, the mole percentage content of the simple substance silicon in the nano silicon metal composite material can be 10-55%, 10-45%, 10-35%, 10-25%, 15-55%, 15-45%, 15-35%, 15-25%, 20-55%, 20-45%, 20-35%, 20-25%, 30-55%, 30-45%, 30-35%, 40-55%, 40-45% or 50-55%.
The second component of the nano silicon metal composite material can comprise a first component of transition metal, or a combination thereof, or a compound formed by the transition metal and the silicon, a second component of aluminum, tin, antimony, or a combination thereof, or a compound formed by the silicon, a third component of alkaline earth elements or a combination thereof, and a fourth component of carbon, oxygen, or a compound formed by the transition metal, the tin, the antimony, or the combination thereof and the silicon, or the compound formed by the transition metal and the silicon. A molar percentage of the second component of at least 10%, at least 15%, at least 20%, at least 25%, or at least 30%; the mole percentage of the second component may also be up to 50%, up to 55%, up to 60%, up to 65%, up to 70%, up to 75%, up to 80%, up to 85%, or up to 90%. Some metals in the second component are electrochemically active and can provide a part of the capacity, while other metals are not electrochemically active, and therefore, the molar percentage of the second component is more preferably 10 to 70%. For example, the second component may be present in an amount of 10 to 20%, 10 to 30%, 10 to 40%, 10 to 50%, 10 to 60%, 10 to 70%, 20 to 30%, 20 to 40%, 20 to 50%, 20 to 60%, 20 to 70%, 30 to 40%, 30 to 50%, 30 to 60%, 30 to 70%, 40 to 50%, 40 to 60% or 40 to 70% by mole.
Silicon-oxygen compound SiO in nano silicon metal composite materialxElemental silicon in the silicon dioxide which is not completely reduced in the raw material or the nano-silicon metal composite material which is the electrolysis product is oxidized again in the post-treatment process, so that the silicon-oxygen compound is attached to the surface of the elemental silicon. The content of the silicon oxide compound in the electrolytic product nano silicon metal composite material can be adjusted by controlling the electrolytic capacity, namely the electrolytic time. If the electrolysis time is controlled to be enough to completely electrolyze the raw material silicon dioxide, the nano silicon metal composite material does not contain silicon oxygen compound. The silicon oxide in the nano silicon metal composite material can embed lithium, and the lithium silicate attached to the surface of the nano silicon formed after lithium embedding has good conductivity and can effectively limit the volume change in the process of lithium embedding and lithium removing of silicon. Therefore, the silicon-oxygen compound in the nano silicon-metal composite material is beneficial to improving the cycle stability of the silicon-metal composite material, but lithium cannot be completely extracted by lithium silicate formed after the silicon-oxygen compound embeds lithium, so that the first coulombic efficiency of the nano silicon-metal composite material is lower. Therefore, the mol percentage of the silicon oxide compound in the nano silicon metal composite material is 0.1-5 mol%.
The nano silicon metal composite material has the following structural characteristics: the metal is one or more of spherical, spheroidal, flaky and linear; the simple substance silicon is in one or more of a linear shape, a granular shape, a tubular shape and a sheet shape. Wherein the simple substance silicon is at least one of nano silicon wire, nano silicon particle, nano silicon tube and nano silicon chip. The particle size of the granular simple substance silicon is less than 100nm, the diameter of the linear simple substance silicon is less than 100nm, the diameter of the tubular simple substance silicon is less than 100nm, and the thickness of the flaky simple substance silicon is less than 100 nm. The simple substance carbon is one or more of spherical shape, similar spherical shape, sheet shape, linear shape and tubular shape. The structure of the nano-silicon metal composite is related to the structure of each component part, and includes but may not be completely consistent with the structure of each component part.
The metal in the nano silicon metal composite material is derived from metal and metal oxide in raw materials and can be in a crystalline and/or amorphous state; the simple substance carbon in the nano silicon metal composite material is derived from a carbon material in the raw material, and can be a graphite negative electrode material commonly used in the field of lithium ion batteries, such as natural graphite, artificial graphite, mesocarbon microbeads and the like; the carbon material may be conductive carbon material for lithium ion battery, such as acetylene black, carbon fiber or carbon tube, etc., or organic pyrolytic carbon, such as polyvinyl alcohol, styrene-butadiene rubber latex, carboxymethyl cellulose, polymethacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, phenolic resin, epoxy resin, glucose, sucrose, fructose, cellulose, starch or asphalt, etc.
The metal in the nano silicon metal composite material and silicon can generate metal silicide, and the metal silicide is mainly generated by slowly soaking the nano silicon and the metal in metal reduction silicon dioxide or molten salt for a long time in the electrode sintering process. The metal silicide can effectively improve the binding force between the simple substance silicon and the metal, improve the conductivity and inhibit the overlarge volume change of the silicon material in the lithium desorption process. Therefore, the uniformity of silicon dioxide and metal materials in the raw materials is ensured, and the generated silicon, metal and metal silicide can be uniformly combined together.
The preparation method of the nano silicon metal composite material provided by the invention comprises the following steps:
1. will consist of metal and metal oxides and silicon dioxideCompounding the porous block with conductive cathode current collector to obtain cathode, using graphite or inert anode as anode, placing at certain temperature with CaCl2Or with CaCl2In the mixed salt melt electrolyte which is mainly used, voltage is applied between a cathode and an anode, and the electrolytic electricity is used as an electrolysis process ending control means, so that the silicon dioxide in the porous block is electrolyzed and reduced into the nano silicon, and the nano silicon metal composite material is prepared at the cathode. The electrolysis time is the electric quantity needed by the theory and above when the electrolysis electric quantity reaches. The theoretically required electric quantity is the electric quantity calculated according to the electrons consumed by SiO2 to become simple substance Si, and the electric quantity changes along with the change of the content of SiO 2.
The structure (such as microscopic uniformity, porosity and pore diameter), composition and size of the porous block body composed of metal, metal oxide and silicon dioxide are key factors influencing the composition proportion, morphology and distribution uniformity of elemental silicon, metal silicide and silicon-oxygen compound of the electrolytic product nano-silicon metal composite material and the specific capacity of the lithium ion battery cathode material. The microscopic uniformity of the metal, the metal oxide and the silicon dioxide in the porous block body consisting of the metal, the metal oxide and the silicon dioxide can directly influence the distribution uniformity of the simple substance silicon, the metal and the metal silicide of the electrolytic product nano silicon metal composite material, so that the porous block body which is uniformly mixed must be manufactured. When the porosity of the porous electric block body consisting of the metal and the silicon dioxide is large, for example, when the porosity of the porous block body is more than 60%, the volume of the silicon generated by electrolytic reduction of the silicon dioxide in the electrolytic process is reduced by 50% due to the release of oxygen, and the porosity of the porous block body consisting of the metal and the silicon is increased after reduction, so that the strength of the porous block body is not enough and the porous block body cannot be completely taken out of the molten salt. When the porosity of the porous block composed of metal and silica is small, for example, when the porosity of the porous block is less than 5 vol%, the pores in the porous block for molten electrolyte calcium chloride to pass through are small, the electrolytic reduction reaction speed is reduced, and the electrolysis time is too long, so that the content of metal silicide in the product is too large.
The specific implementation process of compounding the porous block body consisting of metal, metal oxide and silicon dioxide and the conductive cathode current collector to be used as the cathode comprises the steps of firstly preparing silicon dioxide powder into silicon dioxide colloid, adding the metal and the metal oxide into the silicon dioxide colloid, carrying out high-speed mechanical fusion to ensure that the silicon dioxide is uniformly coated on the metal oxide and the metal to form a mixture, then preparing the mixture into a block green body, forming the porous block body by the block green body at a certain mechanical pressure or a certain temperature, wherein the porous block body is prepared at the mechanical pressure of 10-100 MPa and the temperature of 800-1400 ℃, and the porosity of the obtained porous block body is 10-30%.
2. According to the preparation method of step 1, the metal powder in the raw material is spherical, spheroidal, flaky or linear.
3. According to the preparation method in step 1, the metal oxide in the raw material is in a powder form.
4. According to the preparation method described in step 1, the silica powder refers to silica particles with an average particle size of 10nm to 1 μm.
5. The preparation method according to the step 1, wherein the CaCl is adopted2The main mixed salt melt electrolyte is CaCl2+MY1Wherein M is Ba, Li, Al, Cs, Na, K, Mg, Rb, Be or Sr, Y1Is Cl or F.
6. According to the preparation method of the step 1, the electrolysis voltage is lower than the theoretical decomposition voltage of the electrolyte, and the electrolysis electric quantity is the electric quantity required by the theory and above for the electrolysis electric quantity.
7. According to the preparation method described in step 1, electrolysis is carried out at a temperature of 500-1000 ℃.
8. According to the preparation method of the step 1, after the electrolysis process is finished, the product can be taken out of the molten salt along with the working electrode, and if necessary, a porous block electrode consisting of metal or metal oxide and silicon dioxide can be put in the molten salt to start a new round of electrolysis, so that the continuous production of the nano silicon metal composite material is realized.
9. According to the preparation method of the step 1, after an electrolysis product is taken out, the electrolysis product is cooled to room temperature under an inert atmosphere, and then the electrolysis product is fully washed in water and an organic solvent, and molten salt electrolyte included in the electrolysis product is removed.
10. According to the preparation method described in the step 1, the washed electrolysis product is dried in vacuum for more than 12 hours.
11. According to the preparation method of the step 1, the dried electrolytic product is ground, crushed and sieved to obtain the nano silicon metal composite material.
The following examples illustrate the invention, the "nano SiO" in the raw materials described in the examples2The powder "means a powder having a particle size of 100nm or less.
Example 1
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 30 mol% of spheroidal nickel powder which is sold in the market and has the diameter of 2-10 mu m, 10 mol% of nickel protoxide which is sold in the market and has the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, wherein the porous block is prepared into a porous block body with the mechanical pressure of 14MPa and the temperature of 900 ℃, the porosity of the obtained porous block body is 30 volume percent, and the density is 1.3 g/cm3The conductivity is 0.8 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.2V. After 8 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel-loaded nano silicon particle composite material shown in figure 1, nickel silicide exists between nickel and nano silicon particles discontinuously, and silicon oxide SiO existsxPresent in the surface of nano silicon particlesAnd (5) kneading. The prepared nickel-loaded nano silicon particle composite material contains 38 mol percent of simple substance nickel, 55mol percent of simple substance silicon and nickel silicide (NiSi)2) 5% by mol of a silicon oxide SiO22%, 55 Si/45 (Ni)38(NiSi2)5(giO2)2). The simple substance silicon in the composite material is in a crystalline state, the simple substance silicon is in a granular state and a linear state, the grain diameter of the granular simple substance silicon is less than 100nm, and the diameter of the linear simple substance silicon is less than 100 nm.
The obtained composite material is used for preparing the lithium ion battery electrode according to the following method: the prepared electrolysis product nano silicon-nickel composite material is used as an active substance, Super-P carbon black is used as a conductive agent, PVDF is used as a binder, and the weight ratio of the Super-P carbon black to the PVDF is 7: 2: 1, mixing uniformly, using N-methyl pyrrolidone as a solvent for size mixing, coating the size on copper foil with the thickness of 8 mu m to prepare a pole piece with the thickness of 1.0cm multiplied by 1.5cm, drying at 70 ℃, rolling to the required thickness of the pole piece, and drying for 12 hours at 120 ℃ in vacuum for later use. Using a metal lithium sheet as a counter electrode and a Celgard2300 membrane as a diaphragm, wherein the ratio of the metal lithium sheet to the Celgard2300 membrane is 1 mol/LLIPF6The electrolyte solution is prepared into an experimental battery (the diameter phi is 30mm, and the length L is 100mm) by self design, wherein the volume ratio of the electrolyte solution to the DEC + DMC is 1: 1: 1. The charging and discharging performance of the experimental battery is tested by a blue battery testing system CT2001A tester. The charge-discharge voltage range is 0.005-2.0V, the charge-discharge current density is 80 mA/g, and the capacity retention rate C of the battery for 100 cycles is tested100／C1。
Example 2
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold in the market with the diameter of 2-10 mu m and 20 mol% of nickel protoxide sold in the market with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metallic nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, and preparing the porous block into a porous block with the mechanical pressure of14MPa, the temperature of the porous block body is 900 ℃, and the porosity of the obtained porous block body is 23 volume percent and the density is 1.4 g/cm3The conductivity is 1.2 omega 2 cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.4V. After 7 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 53 Si/47 (Ni)35(NiSi2)8(SiO2)4). As shown in FIG. 3, the crystalline components in the obtained composite material are mainly composed of elemental Si, Ni and NiSi compounds.
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 3
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 20 mol% of spheroidal nickel powder which is commercially available and has the diameter of 2-10 mu m, 30 mol% of nickel protoxide which is commercially available and has the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metallic nickel to form a mixture, then preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 14MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 15 volume percent, and the density of the porous block is 1.25 g/cm3The conductivity is 1.5 omega 2 cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 6 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence and is vacuumizedDrying and sieving to obtain the nickel powder loaded silicon nanowire composite material 45 Si/55 (Ni)48(NiSi)5(SiO2)2)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 4
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 40 mol% of spheroidal nickel powder which is commercially available and has the diameter of 2-10 mu m, 10 mol% of nickel protoxide which is commercially available and has the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metallic nickel to form a mixture, then preparing the mixture into a block green body, forming a porous block by the block green body at a certain mechanical pressure or a certain temperature, wherein the porous block is prepared into a porous block body with the mechanical pressure of 14MPa and the temperature of 900 ℃, the porosity of the obtained porous block body is 29 volume percent, and the density is 1.5 g/cm3The conductivity is 0.4 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 800 deg.C under argon atmosphere, and the cell voltage is 2.8V. After 18 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the composite material 40 Si/60 (Ni) of the nano silicon wire growing on the nickel powder42(NiSi)15(SiO2)3)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 5
60 mol% of sodium with the purity of 99.95 wt%SiO rice2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of commercially available nickel fiber with the diameter of 1-5 mu m, 10 mol% of spherical iron powder and 10 mol% of commercially available nickel protoxide with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on the metal nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 15MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 25 volume percent, and the density of the porous block is 1.1 g/cm3The conductivity is 0.2 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.8V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the silicon metal nanowire composite material 54 Si/46 (Ni)27Fe8(NiSi2)5(FeSi2)2(Fe2O3)2(SiO2)2)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 6
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 12 mol% of nickel fiber with the diameter of 1-5 mu m sold on the market, 20 mol% of spherical iron powder and 8 mol% of nickel protoxide with the purity of 98 wt% sold on the market into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on the metal nickel to form a mixture, then preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, and preparing the porous block into a machineThe mechanical pressure is 20MPa, the temperature for preparing the porous block is 900 ℃, the porosity of the obtained porous block is 15 volume percent, and the density is 1.2 g/cm3The conductivity is 1.2 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.8V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the silicon metal nanowire composite material 52 Si/48 (Ni)18Fe17(NiSi2)3(FeSi2)4(Fe2O3)5(SiO2)1)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 7
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 6 mol% of commercially available nickel fiber with the diameter of 1-5 mu m, 14 mol% of commercially available nickel protoxide with the purity of 98 wt% and 30 mol% of commercially available carbon fiber with the diameter of 20-200 nm and the length of 5-10 mu m into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 20MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block body is 27 volume percent and the density of the obtained porous block body is 0.8 g/cm3The conductivity is 0.2 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaC1 is used2The electrolyte is prepared by performing constant voltage electrolysis at 800 deg.C under argon atmosphere, and the cell voltage is 2.6V. After 22 hours of electrolysisWashing the electrolysis product with water and absolute ethyl alcohol in sequence, drying in vacuum, and sieving to obtain the product 46 Si/26 (Ni) nano silicon metal carbon composite material18(NiSi)48iC3(SiO2)1)／28C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 8
55 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 5 mol% of spheroidal titanium powder sold in the market with the diameter of 2-5 mu m, 10 mol% of titanium dioxide sold in the market with the purity of 98 wt% and 30 mol% of coke with the particle size of 11-15 mu m into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, then preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 10MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block body is 30 volume percent and the density is 1.3 g/cm3The conductivity is 0.5 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.6V. After the electrolysis for 11 hours, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product 53 Si-metal-carbon nano-composite material53／19(Ti12(TiSi2)3SiC3(SiO2)1) and/28C. The simple substance silicon in the composite material is in a crystalline state, the simple substance silicon is in a granular state and a linear state, the grain diameter of the granular simple substance silicon is less than 100nm, and the diameter of the linear simple substance silicon is less than 100 nm. The carbon in the composite material is spherical or quasi-spherical.
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 9
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 4 mol% of spheroidal nickel powder with the diameter of 2-10 mu m sold on the market, 10 mol% of nickel fiber with the diameter of 2-10 m sold on the market, 6 mol% of nickel protoxide with the purity of 98 wt% and 30 mol% of carbon fiber with the diameter of 20-200 nm and the length of 5-10 mu m into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 30MPa, the porous block body preparing temperature of 900 ℃, and obtaining the porous block body with the porosity of 14 vol% and the density of 1.8 g/cm3The conductivity is 0.3 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.6V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product of the nano silicon metal carbon composite material 47Si/25 (Ni)17(NiSi)48iC2(SiO2)2)／28C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 10
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder and stirringForming silica colloid, wherein the mass ratio of water to SiO2 is 2: adding 2 mol% of spherical-like aluminum powder with the diameter of 2-10 mu m, 10 mol% of tin powder with the diameter of 2-10 mu m, 4 mol% of alumina with the purity of 98 wt% and 30 mol% of carbon fiber with the diameter of 20-200 nm and the length of 5-10 mu m into colloid, carrying out high-speed mechanical fusion to ensure that the silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 20MPa, preparing the porous block body into a porous block body with the temperature of 900 ℃, wherein the porosity of the obtained porous block body is 20 volume percent, and the density is 1.1 g/cm3The conductivity is 0.3 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.6V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product 48 Si/24 (Al) nano silicon metal carbon composite material9Sn10SiC3(SiO2)2)／28C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 11
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 10 mol% of commercially available tin powder with the diameter of 2-10 mu m, 5 mol% of titanium dioxide with the purity of 98 wt% and 35 mol% of graphite flakes with the particle size of 3-6 mu m into colloid, mechanically fusing at high speed to ensure that silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, preparing the mixture into a block green body, and forming a porous block green body by the block green body under a certain mechanical pressure or a certain temperatureThe mechanical pressure of the porous block body is 15MPa, the temperature of the porous block body is 900 ℃, and the porosity of the obtained porous block body is 18 volume percent, and the density is 1.4 g/cm3The conductivity is 0.2 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.7V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product of the nano silicon metal carbon composite material 48 Si/81 (Ti)4Sn10(TiSi2)1SiC2(SiO2)2)／33C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 12
20 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 10 mol% of spherical nickel powder with the diameter of 2-10 mu m sold on the market, 5 mol% of titanium dioxide with the purity of 98 wt% and 65 mol% of graphite flake with the particle size of 3-6 mu m into colloid, adding high-speed mechanical fusion to ensure that the silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block with the mechanical pressure of 25MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block is 10 volume percent and the density of the obtained porous block is 1.9 g/cm3The conductivity is 0.1 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere and with voltage regulator controlled voltage of 2.7V3 for 20 hrAfter the decomposition, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the silicon metal carbon nanowire composite material 17 Si/20 (Ti)4Ni8(TiSi)1(NiSi)28iC3(SiO2)2)／63C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 13
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold in the market with the diameter of 2-10 mu m and 20 mol% of nickel protoxide sold in the market with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 30MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 10 volume percent, and the density is 1.6 g/cm3The conductivity is 2.1 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 10 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 50 Si/50 (Ni)35(NiSi)9(SiO2)6)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 14
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold in the market with the diameter of 2-10 mu m and 20 mol% of nickel protoxide sold in the market with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 25MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 15 volume percent, and the density of the porous block is 1.55 g/cm3The conductivity is 1.7 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 9.2 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 51 Si/49 (Ni)35(NiSi)9(SiO2)5)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 15
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder with the diameter of 2-10 mu m sold on the market and 20 mol% of nickel protoxide with the purity of 98 wt% sold on the market into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on the metallic nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, and preparing the porous block into a porous blockThe mechanical pressure is 20MPa, the temperature for preparing the porous block is 900 ℃, the porosity of the obtained porous block is 20 volume percent, and the density is 1.5 g/cm3The conductivity is 1.4 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 8 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 52 Si/48 (Ni)35(NiSi)9(SiO2)4)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 16
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold on the market with the diameter of 2-10 mu m, 10 mol% of nickel protoxide sold on the market with the purity of 98 wt% and 10 mol% of spherical graphite negative electrode material BTR-918 sold on the market into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 15MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block body is 22 volume percent and the density is 1.43 g/cm3The conductivity is 1.4 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 950 deg.C under argon atmosphere and with a voltage regulator at 2.5V. After 7.5 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain nickelPowder-loaded nano-silicon particle composite material 53 Si/37 (Ni)25(NiSi)9(SiO2)3) And 10C. Example 16 a scanning electron microscope image of a silicon-based metal carbon nanowire composite prepared at 950 ℃ is shown in fig. 2.
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 17
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold in the market with the diameter of 2-10 mu m, 19 mol% of nickel protoxide sold in the market with the purity of 98 wt% and 1 mol% of calcium oxide sold in the market with the purity of 99 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metallic nickel to form a mixture, preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block with the mechanical pressure of 20MPa and the temperature of 1000 ℃, wherein the porosity of the obtained porous block is 13 volume percent and the density is 1.56 g/cm3The conductivity is 2.9 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 11 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 50 Si/50 (Ni)35(NiSi)8(CaSi)(SiO2)6)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
The results of the electrochemical performance tests of the examples were compared and are shown in table 1. Compared with the test result, under the same controlled electrolysis condition, the sample with high content of SiO2 in the raw material has higher lithium intercalation capacity for the first time, but the first coulombic efficiency is lower.
TABLE 1 electrochemical Properties of the Nanosilicon carbon composite

Claims (23)

1. The nano silicon metal composite material for the lithium ion battery is characterized by comprising the following components in parts by weight:
(a) the first component is simple substance silicon, and the content of the simple substance silicon is 5-75 mol% relative to the nano silicon metal composite material;
(b) the second component part comprises a metal element, a compound formed by the metal element and silicon and a silicon-oxygen compound, and the content of the second component part is 25-95 mol% relative to the nano silicon composite material;
(c) the third component is simple substance carbon, and the content of the simple substance carbon is 0-70 mol% relative to the nano silicon metal composite material.
2. The nano-silicon metal composite material for the lithium ion battery according to claim 1, wherein the second component of the nano-silicon metal composite material for the lithium ion battery further comprises one or more of a compound formed by a metal element and a metal element, a compound formed by a metal element and carbon, a compound formed by a metal element and oxygen, and a silicon carbon compound.
3. The nano-silicon metal composite material for the lithium ion battery according to claim 1 or 2, wherein the metal element in the second component part is one or more of transition metal elements, aluminum, tin, antimony and alkaline earth elements.
4. The nano-silicon metal composite material for a lithium ion battery according to claim 1, characterized in that: the molar percentage of the simple substance silicon is 10-55 mol%.
5. The nano-silicon metal composite material for a lithium ion battery according to claim 1, characterized in that: the simple substance silicon is one or more of granular, linear, tubular and flaky.
6. The nano-silicon metal composite material for a lithium ion battery according to claim 1, characterized in that: the simple substance silicon is in a crystalline state or/and an amorphous state.
7. The nano-silicon metal composite material for a lithium ion battery according to claim 5, characterized in that: the particle size of the granular simple substance silicon is less than 100nm, the diameter of the linear simple substance silicon is less than 100nm, the diameter of the tubular simple substance silicon is less than 100nm, and the thickness of the flaky simple substance silicon is less than 100 nm.
8. The nano-silicon metal composite material for a lithium ion battery according to claim 1, characterized in that: the simple substance carbon is in one or more of spherical shape, similar spherical shape, sheet shape, linear shape and tubular shape.
9. The nano-silicon metal composite material for a lithium ion battery according to claim 2, characterized in that: the silicon carbon compound SiC of the second component of the nano silicon metal composite material for the lithium ion battery is one or more of granular, linear and flaky.
10. The nano-silicon metal composite material for a lithium ion battery according to claim 9, characterized in that: the grain diameter of the granular SiC is less than 100nm, the diameter of the linear SiC is less than 100nm, and the thickness of the sheet SiC is less than 100 nm.
11. The nano-silicon metal composite material for a lithium ion battery according to claim 3, characterized in that: wherein the transition metal element in the second component is nickel, titanium, iron, copper, cobalt, titanium, manganese, zinc, silver, gold, or a combination thereof.
12. The nano-silicon metal composite material for a lithium ion battery according to claim 3, characterized in that: wherein the alkaline earth element in the second component is magnesium, calcium, strontium, barium, or a combination thereof.
13. The nano-silicon metal composite for a lithium ion battery according to any one of claims 1 to 12, wherein: the silicon metal composite material has a general formula I:
xSi／y(NfHdKe)／zC (I)
wherein,
n is a metal element, and a compound thereof with silicon;
h is one or more of compounds formed by carbon element and one selected from Si and metal elements;
k is one of the compounds of oxygen and Si or one or more of the compounds formed by oxygen and metal elements;
wherein the metal element is one or more of transition metal element, aluminum, tin, antimony and alkaline earth element;
x is the mole percentage of the first component, namely silicon, in the nano silicon metal composite material, and the x is 5-75 mol%;
y is the mole percentage of the second component in the nano silicon metal composite material, and y is 25-95 mol%;
z is the mole percentage of carbon in the nano silicon metal composite material, and z is 0-70 mol%;
wherein x + y + z is 100 mol%;
f, d, e are the mole percentages of N, H and K in the second component part, respectively; f is 10-90 mol%: d is 0-10 mol%: e is 10 to 90 mol%, and f + d + e is 100 mol%.
14. A method for preparing the nano-silicon metal composite material for the lithium ion battery of any one of claims 1 to 13, which is characterized in that: using a porous block consisting of silicon dioxide powder containing at least metal M or metal oxide MO as a cathode, graphite or an inert anode as an anode, CaCl2Or with CaCl2And (2) taking the mixed salt melt as a main electrolyte to form an electrolytic bath, applying direct current voltage between a cathode and an anode, and controlling the electrolytic current density and electrolytic electric quantity to ensure that the silicon dioxide or the silicon dioxide and the metal oxide in the porous block are subjected to in-situ electrolytic reduction at the cathode to prepare the nano silicon metal composite material for the lithium ion battery, wherein M is one or more elements selected from transition metal elements, aluminum, tin, antimony and alkaline earth elements.
15. The method of claim 14, wherein: the porous block may also contain carbon.
16. The method of claim 15, wherein: the porous block body composed of the silicon dioxide powder at least containing the metal M or the metal oxide MO is formed by preparing the silicon dioxide powder into silicon dioxide colloid, uniformly coating the silicon dioxide colloid on one or two of the metal M and the metal oxide MO to form a mixture, and preparing the mixture into the porous block body.
17. The method of claim 16, wherein: and uniformly coating the silicon dioxide colloid on one or two of the metal M and the metal oxide MO and the carbon.
18. The method of claim 14, wherein: the porous block body composed of the silicon dioxide powder at least containing the metal M or the metal oxide MO is formed by preparing the silicon dioxide powder into silicon dioxide colloid, uniformly coating the silicon dioxide colloid on one or two of the metal M and the metal oxide MO to form a mixture, and preparing the mixture into the porous block body.
19. The method of claim 18, wherein: and uniformly coating the silicon dioxide colloid on one or two of the metal M and the metal oxide MO.
20. The method of claim 14, wherein: the particle size of the silicon dioxide powder is 10nm to 1 mu m.
21. The method of claim 14, wherein: the porosity of the porous block is 1-40 vol%.
22. The method of claim 21, wherein: the porosity of the porous block is 10-30 vol%.
23. A lithium ion battery, the battery includes positive pole, negative pole and nonaqueous electrolyte, characterized by that: the negative electrode comprises the nano-silicon metal composite material as claimed in any one of claims 1 to 13.
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