CN112820847A - Silicon-based negative electrode material and preparation method thereof, lithium ion battery and electric appliance - Google Patents

Silicon-based negative electrode material and preparation method thereof, lithium ion battery and electric appliance Download PDF

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CN112820847A
CN112820847A CN202011630980.5A CN202011630980A CN112820847A CN 112820847 A CN112820847 A CN 112820847A CN 202011630980 A CN202011630980 A CN 202011630980A CN 112820847 A CN112820847 A CN 112820847A
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silicon
negative electrode
electrode material
preparation
copper
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谢迎春
赵仕杰
马扬洲
黄仁忠
曾良
王高民
张科杰
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Institute of New Materials of Guangdong Academy of Sciences
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/134—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
    • H01M4/13—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
    • H01M4/36—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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

The invention discloses a silicon-based negative electrode material, a preparation method thereof, a lithium ion battery and an electric appliance. Relates to the technical field of battery electrode material preparation. The preparation method of the silicon-based negative electrode material comprises the following steps: and (3) annealing the primary cathode material with the Si-Cu coating loaded on the surface, which is obtained by cold spraying, at 500-800 ℃ in an inert gas atmosphere, and preserving heat for 7-9 hours. The silicon-based negative electrode material is prepared by the preparation method. The lithium ion battery adopts the silicon-based negative electrode material as a negative electrodeAnd (4) a pole. The electric appliance takes the lithium ion battery as a power supply. The primary cathode material of the Si-Cu coating is obtained by cold spraying on the copper foil, and then the Si-Cu is obtained by annealing treatment at proper temperature and heat preservation time3The Si-Cu composite material has good cycle stability and reversible capacity when being used as a negative electrode material of a lithium ion battery.

Description

Silicon-based negative electrode material and preparation method thereof, lithium ion battery and electric appliance
Technical Field
The invention relates to the technical field of preparation of battery electrode materials, in particular to a silicon-based negative electrode material and a preparation method thereof, a lithium ion battery and an electric appliance.
Background
With the increasing prominence of environmental and energy problems, the development of new clean energy to replace old energy has been urgent. The development and utilization of new energy needs corresponding energy storage equipment to be well applied to various industries. Lithium ion batteries are currently considered to be one of the most promising energy storage devices. The lithium ion battery has the advantages of high specific energy, high safety performance, wide working temperature range, long storage life and the like, is widely applied to various small-sized mobile devices, and is also very suitable to be used as a power supply of an electric automobile and a large-sized power storage standby power supply. In particular, in the development of new energy vehicles, further improvements in energy density, power density, cycle life, and the like of lithium ion batteries are required. This depends to a large extent on the electrode material of the lithium ion battery, and the capacity of the electrode material directly affects the specific energy of the battery.
The lithium ion battery cathode material which is commercially applied at present is mainly graphite, but the theoretical specific capacity of the graphite material is low (about 372mAh/g), and the application requirement of the high-energy lithium ion battery cannot be met. Therefore, the development of new lithium ion battery negative electrode materials to replace graphite negative electrodes has been slow. Li in silicon-based alloy22Si5Has the maximum lithium storage capacity and the theoretical specific capacity as high as 4200 mAh/g. Silicon has a moderate lithium intercalation/deintercalation potential (about 0.4V), better than graphiteThe lithium ion battery cathode material is a very promising lithium ion battery cathode material. However, the disadvantages of silicon anode materials are also quite significant, such as: (1) in the process of lithium ion intercalation and deintercalation, the silicon negative electrode material can generate violent volume expansion (100-300 percent), and the huge volume effect is easy to damage the material structure, so that the reversibility is poor. (2) A Solid Electrolyte Interface (SEI) film continuously grows/pulverizes on a new surface of the silicon negative electrode, consuming a large amount of lithium ions, resulting in a large irreversible capacity, and finally causing a reduction in initial coulombic efficiency. (3) The low conductivity of silicon leads to rapid degradation of the electrodes and correspondingly limits their development. Overcoming the volume effect and enhancing the conductivity of silicon materials has therefore become a research focus in the field, and so far, the volume expansion of silicon has been weakened mainly by nanocrystallization or recombination of silicon.
The electrode manufacturing process for lithium ion batteries includes coating a slurry onto a metallic current collector, wherein the slurry comprises a mixture of an active material, a conductive agent, and a binder. However, the use of devices such as flexible batteries in flexible electronic devices has been limited due to imperfections in the electrode materials and manufacturing processes. The conventional lithium ion battery electrode is required to be applied to a battery with strong flexibility, and various problems need to be solved. The first problem is that the interface between the electrode material and the current collector is only point-contacted by the binder particles, and thus the adhesion is weak. The electrode having weak adhesion may generate cracks and delamination at an interface due to deformation in a bent/flexed state and volume expansion during repeated charge and discharge, thereby causing a loss of capacitance and a decrease in performance. The binder (about 5-10% of the total weight of the electrode) is not electrochemically active and cannot store lithium ions, thereby reducing the total weight. In addition, the addition of the binder leads to an increase in the internal resistance of the electrode and a decrease in electrochemical performance. The irreversible capacity increases with increasing binder content of the electrode material. These problems, such as adhesion between the electrode paste and the current collector, have been major constraints in developing fully flexible lithium ion batteries. Therefore, a new process that can compensate for the capacity loss due to the binder while ensuring high adhesion will enable flexible electrode fabrication. Here we describe a new method for the preparation of additive-free electrodes of silicon-based materials using a supersonic kinetic spray technique and successfully demonstrated their combination with flexible lithium ion batteries. The supersonic kinetic spray gives high energy to the particles and enables direct coating and self-healing. Because the method increases the bonding energy without using any bonding agent, the novel electrode preparation process can promote the development of the flexible lithium ion battery and has wide application prospect.
Because the silicon powder has poor conductivity and large volume change during circulation, in order to improve the conductivity and the circulation stability of the silicon powder serving as the cathode of the lithium ion secondary battery, the supersonic speed power spraying technology is adopted to fully mix the silicon powder and the copper powder, the nitrogen with high temperature and high pressure is used as a carrier, the speed of spraying particles is accelerated by a convergent-divergent nozzle, the sprayed particles reach 300-1200 m/s, the particles impact the surface of a matrix at high speed in a solid state, and a coating is formed mainly by large plastic deformation. However, since silicon is a semiconductor material, it is brittle and hard in nature, and is inferior in plastic deformability to metal, the deposition rate is inferior to that of metal. If the silicon-copper mixed powder is deposited on a substrate, because the deposition effect of the bare silicon powder on the surface of the deposition layer on the copper substrate is not ideal, the surface modification is needed to be carried out on the interface of silicon particles and copper particles so as to prevent the active silicon from falling off from the surface of the copper supporting substrate due to the serious volume change of the silicon particles in the circulating process, and the long-term circulating performance is still not ideal.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a silicon-based negative electrode material, a preparation method thereof, a lithium ion battery and an electric appliance.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing a silicon-based negative electrode material, comprising:
and (3) placing the primary cathode material with the surface loaded with the Si-Cu coating obtained by cold spraying in a tubular furnace at the temperature of 500-800 ℃ and under the inert gas atmosphere for annealing, and preserving heat for 7-9 h.
In an alternative embodiment, the annealing further comprises:
and (3) carrying out cold spraying on the surface of the substrate by adopting silicon-copper mixed powder to obtain the primary cathode material with the surface loaded with the Si-Cu coating.
In an alternative embodiment, the substrate is a copper foil.
In an optional embodiment, the copper foil has a thickness of 0.04 to 0.08 mm.
In an alternative embodiment, the mass ratio of silicon to copper in the silicon-copper mixed powder is 4-9: 6-1.
In an optional embodiment, the thickness of the copper foil selected for the substrate is approximately 0.04-0.08 mm.
In an alternative embodiment, the equipment process parameters are set during cold spraying as follows: the gas pressure is 3-4 MPa, the gas flow rate is 2-4 ml/min, and the gas temperature is 600-800 ℃.
In an alternative embodiment, the distance from the nozzle to the substrate is set to be 20-40 cm during cold spraying.
In an optional embodiment, the scanning speed is 150-200 mm/s during cold spraying, the powder feeding amount is 200-300 g/min, and the nozzle scans the surface of the copper foil substrate back and forth once respectively to obtain the primary cathode material of the Si-Cu coating.
In an alternative embodiment, the silicon-copper mixed powder is obtained by mixing copper powder and silicon powder, wherein the particle size of the copper powder is less than 15 microns, and the particle size of the silicon powder is less than or equal to 5 microns.
In a second aspect, the embodiment of the invention provides a silicon-based negative electrode material, which is prepared by the preparation method provided by the embodiment of the invention.
In a third aspect, an embodiment of the present invention provides a lithium ion battery, where the silicon-based negative electrode material provided in the embodiment of the present invention is used as a negative electrode.
In a fourth aspect, an embodiment of the present invention provides an electrical appliance, where the lithium ion battery provided in the embodiment of the present invention is used as a power source.
The invention has the following beneficial effects:
the primary cathode material of the Si-Cu coating is obtained by cold spraying on the copper foil, and then the Si-Cu is obtained by annealing treatment at proper temperature and heat preservation time3The Si-Cu composite material has good cycle stability and reversible capacity when being used as a negative electrode material of a lithium ion battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a technical schematic diagram of cold spraying;
FIG. 2 is a schematic view of a negative electrode material obtained in example 1;
FIG. 3 is a field emission scanning electron micrograph of a cross section of a negative electrode material prepared in example 1;
FIG. 4 is a SEM image of the surface of the anode material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The silicon-based negative electrode material and the preparation method thereof, the lithium ion battery and the electric appliance provided by the embodiment of the invention are specifically described below.
A preparation method of a silicon-based anode material comprises the following steps:
and (3) annealing the primary cathode material which is obtained by cold spraying and is loaded with the Si-Cu coating on the surface at 500-800 ℃ in an inert gas atmosphere, and preserving heat for 7-9 h.
Annealing the primary negative electrode material cold sprayed (i.e., kinetic spray at supersonic velocity) to obtain a Si-Cu coating in a tube furnace under an inert atmosphere can greatly inhibit the detachment of silicon particles and copper particles, thereby providing better cycle performance.The improvement in the interfacial stability of the annealed samples is mainly due to the formation of Cu at the interface3In the Si alloy phase, Cu atoms diffuse into Si particles. Conductive and inactive Cu formed in silicon3Si phase as buffer medium, highly conductive Cu3Si has excellent mechanical flexibility and high electronic conductivity, and can slow down structural degradation and provide high conductivity. The Si-Cu3Si-Cu composite material obtained by annealing treatment at a proper temperature and a proper heat preservation time has good cycle stability and reversible capacity when being used as a negative electrode material of a lithium ion battery.
The principle that the negative electrode material prepared by the preparation method provided by the invention has high cycle performance and conductivity mainly comprises the following three points:
1. the coating formed on the substrate is dense and has low porosity. In the spraying process, the impact of the subsequent particles plays a role in tamping a coating formed by the previous particles, the volume shrinkage is not obvious, the low porosity is ensured, the electrolyte can be effectively prevented from permeating into the inside and contacting with the active material to form an SEI film, and the irreversible capacity is effectively reduced.
2. Due to the large contact area inside the coated particles and at the interface between the coating and the current collector (substrate), it exhibits better adhesion than electrodes made by conventional slurry methods, without the tendency to undergo volumetric changes during the silicon charge-discharge cycle, which can lead to silicon falling off the current collector.
3. Compared with a bare silicon electrode, the stability of the sample at the phase interface after annealing is mainly improved by Cu on the interface3The formation of Si phase and the diffusion of Cu to Si particles provide better cyclability, and Cu3Si has excellent mechanical flexibility and high electronic conductivity, and provides an electron transfer channel.
Compared with the prior art, the preparation method provided by the invention has the following technical effects:
1. the cold spraying technology is a new material surface modification technology which is simple and convenient to operate, safe, pollution-free and capable of quickly preparing a coating. It can be prepared at normal temperature or lower temperature.
2. The powder particles of the spray material are accelerated in a hot, non-oxidizing gas stream and the coating is substantially free of oxidation and has a low porosity.
3. Because the speed is high when the particles impact the substrate, larger plastic deformation can be generated, so that the inside of the coating and the current collector are tightly combined, the coating is not easy to crack, and the flexible bending state is achieved.
4. No acid washing, no toxicity, no pungent smell and other organic solvent and gas are involved and exhausted during synthesis, and this is favorable to environment protection in industrial production.
The preparation method provided by the invention specifically comprises the following steps:
and S1, uniformly mixing the copper powder and the silicon powder, and placing the mixture into a powder feeder of cold spraying equipment.
Preferably, in order to make the coating performance better, the particle size of the copper powder is less than 15 μm, and the particle size of the silicon powder is less than or equal to 5 μm.
Preferably, in order to ensure that the prepared negative electrode material has better cycle performance and reversible capacity, the mass ratio of silicon to copper in the silicon-copper mixed powder is 4-9: 6-1.
S2, setting equipment process parameters during cold spraying as follows: the gas pressure is 3-4 MPa, the gas flow rate is 2-4 ml/min, the gas temperature is 600-800 ℃, the scanning speed is 150-200 mm/s, and the powder feeding amount is 200-300 g/min. And setting the distance from the nozzle to the substrate to be 20-40 cm during cold spraying.
Preferably, the feed gas is nitrogen.
S3, preheating the feeding powder, and heating and pressurizing the feeding gas. The step is the prior art and can be carried out by conventional operation.
And S4, starting the cold spraying device to perform cold spraying on the substrate, and scanning the nozzle back and forth on the surface of the substrate to obtain the primary cathode material with the Si-Cu coating, wherein the thickness of the primary cathode material with the Si-Cu coating is about 60 mu m. The technical schematic diagram of cold spraying is shown in fig. 1.
Preferably, in order to enable the negative electrode material to have better performance, the substrate is a copper foil; more preferably, the copper foil has a thickness of 0.04 to 0.08 mm.
S5, placing the copper foil piece of the primary cathode material with the Si-Cu coating in a tube furnace, filling inert gas in the tube furnace, controlling the temperature in the tube furnace to be 500-800 ℃ under the atmosphere of the inert gas, and annealing the copper foil piece of the primary cathode material with the Si-Cu coating in the tube furnace for 7-9 hours.
The silicon-based negative electrode material provided by the embodiment of the invention is prepared by the preparation method provided by the embodiment of the invention.
The lithium ion battery provided by the embodiment of the invention adopts the silicon-based negative electrode material provided by the embodiment of the invention as a negative electrode. For example, a CR2025 button cell, is prepared as follows:
1. the copper foil of the silicon-based negative electrode material prepared by the embodiment of the invention is cut into electrode slices with the diameter of 13mm, and the electrode slices are weighed and transferred into a glove box in argon atmosphere for standby.
2. A lithium cell was assembled in a glove box filled with argon, the positive and negative electrode cases were of type CR2025, the separator was a polypropylene film, the electrolyte was 1M LiPF6 in ethylene carbonate/diethyl carbonate (1:1 vol%), with 10% fluoroethylene carbonate) as the electrolyte, and other parts required for the cell were a spring plate and a gasket. The electrode plate of the silicon-based negative electrode material is a working electrode, and the metal lithium plate is used as a counter electrode to assemble the button cell with the model number of CR 2025.
The embodiment of the invention provides an electric appliance, and the lithium ion battery provided by the embodiment of the invention is used as a power supply.
The features and properties of the present invention are described in further detail below with reference to examples.
In the following examples and comparative examples, copper foil having a thickness of 0.05mm was selected as a substrate in the preparation of the negative electrode material.
Example 1
The preparation method of the silicon-based anode material provided in this embodiment is performed according to the specific steps described in the above, specifically:
the mass ratio of silicon to copper in the silicon-copper mixed powder is 8: 2.
The technological parameters during cold spraying are as follows: the gas pressure is 4MPa, the gas flow rate is 3ml/min, and the gas temperature is 800 ℃; the scanning speed is 200mm/s, and the powder feeding amount is 200 g/min.
The annealing temperature is 600 ℃, and the heat preservation time is 9 h.
Example 2
The preparation method of the silicon-based anode material provided in this embodiment is performed according to the specific steps described in the above, specifically:
the mass ratio of silicon to copper in the silicon-copper mixed powder is 8: 2.
The technological parameters during cold spraying are as follows: the gas pressure is 3MPa, the gas flow rate is 3ml/min, and the gas temperature is 800 ℃; the scanning speed is 200mm/s, and the powder feeding amount is 200 g/min.
The annealing temperature is 600 ℃, and the heat preservation time is 9 h.
Example 3
The preparation method of the silicon-based anode material provided in this embodiment is performed according to the specific steps described in the above, specifically:
the mass ratio of silicon to copper in the silicon-copper mixed powder is 8: 2.
The technological parameters during cold spraying are as follows: the gas pressure is 4MPa, the gas flow rate is 3ml/min, and the gas temperature is 600 ℃; the scanning speed is 200mm/s, and the powder feeding amount is 200 g/min.
The annealing temperature is 600 ℃, and the heat preservation time is 9 h.
Example 4
The preparation method of the silicon-based anode material provided in this embodiment is performed according to the specific steps described in the above, specifically:
the mass ratio of silicon to copper in the silicon-copper mixed powder is 8: 2.
The technological parameters during cold spraying are as follows: the gas pressure is 3MPa, the gas flow rate is 3ml/min, and the gas temperature is 600 ℃; the scanning speed is 200mm/s, and the powder feeding amount is 200 g/min.
The annealing temperature is 600 ℃, and the heat preservation time is 9 h.
Example 5
The preparation method of the silicon-based anode material provided in this embodiment is substantially the same as that of embodiment 1, and the difference is only that:
the mass ratio of silicon to copper in the silicon-copper mixed powder is 6.36: 3.64.
Example 6
The preparation method of the silicon-based anode material provided in this embodiment is substantially the same as that of embodiment 1, and the difference is only that:
the mass ratio of silicon to copper in the silicon-copper mixed powder is 5.05: 4.95.
Examples 7 to 9
Examples 7 to 9 provide a method of preparing a silicon-based anode material substantially the same as in example 1, except that: the annealing temperatures were 500 ℃, 700 ℃ and 800 ℃, respectively.
Comparative example 1
This comparative example is essentially the same as example 1 except that: replacing the silicon-copper mixed powder with the same amount of bare silicon powder.
Comparative example 2
This comparative example is essentially the same as example 1 except that: no annealing treatment is performed.
Examples of the experiments
The cathode materials prepared by the preparation methods provided in examples 1 to 9 and comparative examples 1 and 2 were used as cathodes to prepare CR2025 coin cells, respectively, according to the assembly method of the CR2025 coin cell described above. The resulting CR2025 was tested for performance.
The half cell needs to be kept stand for 24h before testing.
The used equipment is a NEWARE-BTS-5V/10mA battery test system, the voltage test range is 0.01-1.5V, and the current density of the cycle life is 100 mA/g. The EIS test of the samples was carried out using a Wuhan Consted electrochemical workstation with a wave amplitude of 5mV and a frequency range of 10-2～105Hz. The test results are recorded in table 1.
TABLE 1 Battery Performance for each group
Figure BDA0002880045490000101
As can be seen from the above table, the battery made of the negative electrode material prepared by the preparation method provided by the embodiments of the present invention has excellent performance, and has good cycle performance and reversible capacity. The performance of the battery made of the negative electrode material prepared by the comparative example is obviously inferior to that of the battery made of the comparative example.
Experimental example 2
Microstructure observation was performed on the anode material obtained in example 1, and fig. 2 to 4 were obtained. From fig. 2-4, it can be seen that the coating is dense, the coating is tightly bonded with the substrate, and the coating is not easy to crack.
In summary, according to the preparation method of the silicon-based negative electrode material provided by the invention, the primary negative electrode material of the Si-Cu coating is obtained by cold spraying on the copper foil with the thickness of 0.05mm, and then annealing treatment is carried out at a proper temperature for a proper heat preservation time to obtain the Si-Cu3The Si-Cu composite material has good cycle stability and reversible capacity when being used as a negative electrode material of a lithium ion battery.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a silicon-based negative electrode material is characterized by comprising the following steps:
and (3) annealing the primary cathode material with the Si-Cu coating loaded on the surface, which is obtained by cold spraying, at 500-800 ℃ in an inert gas atmosphere, and preserving heat for 7-9 hours.
2. The method for preparing the silicon-based anode material according to claim 1, wherein the annealing further comprises:
carrying out cold spraying on the surface of the substrate by adopting silicon-copper mixed powder to obtain a primary cathode material with a Si-Cu coating loaded on the surface;
preferably, the substrate is a copper foil; more preferably, the thickness of the copper foil is 0.04-0.08 mm.
3. The preparation method of the silicon-based negative electrode material according to claim 2, wherein the mass ratio of silicon to copper in the silicon-copper mixed powder is 4-9: 6-1.
4. The preparation method of the silicon-based anode material as claimed in claim 2, wherein the equipment process parameters are set as follows during cold spraying: the gas pressure is 3-4 MPa, the gas flow rate is 2-4 ml/min, and the gas temperature is 600-800 ℃.
5. The method for preparing the silicon-based anode material as claimed in claim 2, wherein the distance from the nozzle to the substrate is set to be 20-40 cm during cold spraying.
6. The preparation method of the silicon-based anode material according to claim 2, wherein the scanning speed during cold spraying is 150-200 mm/s, the powder feeding amount is 200-300 g/min, and the nozzle scans the surface of the substrate back and forth once respectively to obtain the silicon-copper primary anode material.
7. The method for preparing the silicon-based negative electrode material as claimed in claim 2, wherein the silicon-copper mixed powder is obtained by mixing copper powder and silicon powder, the particle size of the copper powder is less than 15 μm, and the particle size of the silicon powder is less than or equal to 5 μm.
8. A silicon-based negative electrode material is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. A lithium ion battery, characterized in that the silicon-based negative electrode material according to claim 8 is used as a negative electrode.
10. An electrical appliance characterized by the lithium ion battery according to claim 9 as a power source.
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