CN115196636A - Metal-doped silicon-based negative electrode material and preparation method and application thereof - Google Patents
Metal-doped silicon-based negative electrode material and preparation method and application thereof Download PDFInfo
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- CN115196636A CN115196636A CN202211119409.6A CN202211119409A CN115196636A CN 115196636 A CN115196636 A CN 115196636A CN 202211119409 A CN202211119409 A CN 202211119409A CN 115196636 A CN115196636 A CN 115196636A
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/035—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition or reduction of gaseous or vaporised silicon compounds in the presence of heated filaments of silicon, carbon or a refractory metal, e.g. tantalum or tungsten, or in the presence of heated silicon rods on which the formed silicon is deposited, a silicon rod being obtained, e.g. Siemens process
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- H01M4/36—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
- 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 relates to a metal-doped silicon-based negative electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: connecting a metal wire between two electrodes arranged in an explosion reaction chamber; vacuumizing the explosion reaction chamber, and introducing quantitative gaseous siloxane material; the capacitor is charged, when the voltage at two ends of the capacitor exceeds the voltage critical value of the gap gas switch, the gap gas switch is switched on, high-energy electric pulses are generated through the discharge of the capacitor, the metal wires are evaporated and exploded to form nano metal particles, the nano metal particles collide with gaseous siloxane materials in an explosion reaction chamber for heat exchange, the siloxane materials are cracked to form silicon oxides, and the nano metal particles reduce the silicon oxides and grow through nucleation to form metal doped materials.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a metal-doped silicon-based negative electrode material and a preparation method and application thereof.
Background
The commercial power battery cathode material is mainly graphite, but the theoretical gram capacity of the graphite is low, the requirement of a high-specific-capacity lithium ion power battery cannot be met, and in the high-capacity cathode material, a silicon-based material has very high capacity, wherein, the silicon oxide (SiO) is used as a next-generation novel cathode material, so that the power battery cathode material has the characteristics of high capacity, low expansion, long service life and the like, and the cruising ability of consumer electronic products and electric automobiles can be effectively improved. However, the practical use of silica is limited by its low first-pass efficacy.
At present, the common method for solving the technical problems is to add metal magnesium and reduce silicon monoxide by magnesium so as to improve the first effect.
The method for preparing the anode material by reducing the silicon oxide by magnesium generally adopts a solid state sintering mode. For example, the negative electrode material is prepared by adding silica to magnesium powder and sintering, and then acid-washing the product. For another example, the negative electrode material is prepared by sintering the silicon monoxide in an inert gas at a high temperature to obtain disproportionated silicon monoxide, adding magnesium powder for sintering, and then pickling the product. The method needs a high-temperature calcination process and then subsequent treatment, the process time is long, and the bulk phase doping formed by calcining the solid-phase material is difficult to achieve uniform effect and the performance of the material is difficult to fully exert.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a metal-doped silicon-based negative electrode material. The metal wire is gasified by adopting an electric explosion method and exchanges heat with siloxane gas to generate cracking and reduction reactions, and the metal wire is nucleated and cooled to form the anode material uniformly doped with metal.
In a first aspect, an embodiment of the present invention provides a preparation method of a metal-doped silicon-based anode material, where the preparation method includes:
connecting a metal wire between two electrodes arranged in an explosion reaction chamber; one end electrode is connected to one end of the capacitor through the gap gas switch, and the other end electrode is connected to the other end of the capacitor;
vacuumizing the explosion reaction chamber, and introducing quantitative gaseous siloxane material;
the capacitor is charged, when the voltage at two ends of the capacitor exceeds the voltage critical value of the gap gas switch, the gap gas switch is switched on, high-energy electric pulses are generated through the discharge of the capacitor, the metal wires are evaporated and exploded to form nano metal particles, the nano metal particles collide with gaseous siloxane materials in the explosion reaction chamber for heat exchange, the siloxane materials are cracked to form silicon oxides, and the nano metal particles reduce the silicon oxides and grow through nucleation to form metal doped materials.
Preferably, the metal doped material is sintered in an inert gas atmosphere, the material obtained by sintering is subjected to carbon coating treatment, and the silicon-based negative electrode material doped with the metal is obtained by hierarchical demagnetization.
Preferably, the cracking of the siloxane to form silicon oxide specifically comprises:
the siloxane absorbs the heat energy released by the metal wire evaporation, and obtains the energy generated by the collision heat exchange between the nanometer metal particles and the siloxane in the explosion reaction chamber, and the nanometer metal particles are cracked to form silicon oxide.
Preferably, the silicone material specifically includes silicone and derivatives thereof;
the material of the metal wire comprises: one or more of magnesium, aluminum, lithium, sodium, titanium, zinc, iron, chromium, nickel, molybdenum, tin, germanium, calcium or copper; the diameter of the metal wire is 0.1-10 μm; the length is 10mm-200mm.
Preferably, the capacitor is charged such that the voltage of the capacitor is 5kV-100kV.
Further preferably, the sintering temperature is 600-1000 ℃, and the sintering time is 2-12 hours.
In a second aspect, an embodiment of the present invention provides a metal-doped silicon-based negative electrode material prepared by the method for preparing a silicon-based negative electrode material according to the first aspect.
In a third aspect, an embodiment of the present invention provides a negative electrode material for a lithium battery, including the metal-doped silicon-based negative electrode material according to the second aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium battery pole piece, including the negative electrode material of the lithium battery described in the third aspect.
In a fifth aspect, an embodiment of the present invention provides a lithium battery, including the lithium battery pole piece described in the fourth aspect.
The preparation method of the metal-doped silicon-based negative electrode material provided by the invention is characterized in that an electric explosion method is adopted to gasify a metal wire, and the metal wire is subjected to heat exchange with siloxane gas to generate cracking and reduction reactions, and nucleation and cooling are carried out to form the metal-uniformly-doped negative electrode material. The electric explosion method adopted by the invention has rapid energy explosion and short preparation time, and because the extreme condition of the electric explosion method provides a thermodynamic unbalanced structure for the nano metal particles and stores redundant energy, the nano metal particles obtained by explosion have high activity, silicon oxide can be fully reduced, the nucleated silicon crystal particles are controllable, and the metal elements are uniformly doped.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a schematic structural diagram of a preparation apparatus for preparing a metal-doped silicon-based anode material according to an embodiment of the present invention;
fig. 2 is a flowchart of a method for preparing a metal-doped silicon-based negative electrode material according to an embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it will be understood that these examples are given solely for the purpose of illustration and are not to be construed as limiting the invention in any way, i.e., not as limiting the scope of the invention.
The invention provides a preparation method of a metal-doped silicon-based negative electrode material, which is used for preparing the silicon-based negative electrode material by an electric explosion method. In order to better understand the preparation method of the present invention, a brief description will be given first of all to a preparation apparatus used for the preparation.
Fig. 1 is a schematic structural diagram of a preparation apparatus for preparing a metal-doped silicon-based anode material according to an embodiment of the present invention. As shown in the figure, the device mainly comprises: high voltage generator 1, high voltage capacitor 2, gap gas switch 3, electrode 4, explosion reaction chamber 5, gas supply device 6 and vacuum pump 7.
The high-voltage generator 1 is connected to two ends of the high-voltage capacitor 2 and used for charging the high-voltage capacitor 2, so that the voltage of the high-voltage capacitor 2 can be charged to 5kV-100kV and reaches or exceeds the switch-on critical voltage of the gap gas switch 3.
The metal wire 8 is connected between the two electrodes 4 arranged in the explosion reaction chamber 5; one end electrode of the two electrodes is connected to one end of the high-voltage capacitor 2 through the gap gas switch 3, and the other end electrode is connected to the other end of the high-voltage capacitor 2.
The material of the wire 8 usable in the present production method may include: one or more of magnesium, aluminum, lithium, sodium, titanium, zinc, iron, chromium, nickel, molybdenum, tin, germanium, calcium or copper; the diameter of the metal wire is preferably 0.1 μm to 10 μm; the length is preferably 10mm to 200mm.
In a preferred embodiment, the wire 8 may be fixedly mounted between the two electrodes in the explosion chamber 5 by means of an automatic wire supply system. The existing equipment can be realized and is not explained again. Of course, manual fixed mounting is also possible.
By switching on the gap gas switch 3, the high-voltage capacitor 2 can discharge to generate high-energy electric pulse metal wires to evaporate and explode to form nano metal particles.
The gas supply device 6 and the vacuum pump 7 are respectively connected to the explosion reaction chamber 5, the vacuum pump 7 is used for vacuumizing the explosion reaction chamber 5, and the gas supply device 6 is used for introducing quantitative gaseous siloxane materials into the explosion reaction chamber 5.
Based on the above preparation apparatus, the preparation method of the metal-doped silicon-based anode material provided by the invention is shown in fig. 2, and mainly comprises the following steps:
and step 110, connecting a metal wire between two electrodes arranged in the explosion reaction chamber.
One end electrode of the metal wire is connected to one end of the capacitor through the gap gas switch, and the other end electrode of the metal wire is connected to the other end of the high-voltage capacitor; the material of the wire includes: one or more of magnesium, aluminum, lithium, sodium, titanium, zinc, iron, chromium, nickel, molybdenum, tin, germanium, calcium or copper; the diameter of the metal wire is 0.1-10 μm; the length is 10mm-200mm.
specifically, the silicone material specifically includes silicone and derivatives thereof.
In a specific embodiment, the volume of the explosion reaction chamber is 0.1m 3 And introducing siloxane gas until the pressure in the explosion reaction chamber is 1 standard atmosphere.
specifically, the high-voltage capacitor is charged, so that the electrode voltage reaches or exceeds the electrode breakdown voltage minimum critical value, gas in the gap gas switch breaks down, the switch loses insulativity, the switch is switched on, at the moment, high-energy electric pulses act on the metal wire through the electrode, electric energy is converted into internal energy of the metal wire, and the metal wire is evaporated and exploded.
The evaporation of the wire gives off a large amount of heat energy. The siloxane absorbs the heat energy released by the metal wire evaporation, and obtains the energy generated by the collision heat exchange between the nano metal particles and the siloxane in the explosion reaction chamber, and the nano metal particles are cracked to form silicon oxide.
Because the extreme condition of the electric explosion method provides a thermodynamic unbalanced structure for the nano metal particles and stores redundant energy, the nano metal particles obtained by explosion have high activity and can effectively and fully reduce silicon oxide to form simple substance silicon.
And nucleating and cooling the elemental silicon and the gaseous substance in the explosion reaction chamber to form the anode material uniformly doped with the metal. In the final product nucleated with silicon, magnesium silicate is present in addition to silicon, and in some embodiments, unreduced silicon oxide may also be present.
And 140, sintering the metal doped material in an inert gas atmosphere to obtain the metal doped silicon-based negative electrode material.
Through sintering, the nano metal particles can fully reduce the silicon oxide.
In specific implementation, the sintering temperature is 600-1000 ℃, and the sintering time is 2-12 hours.
The sintering temperature and time are lower and shorter than those of the prior art, in which the solid material is directly mixed and sintered, because the nano-metal particles already undergo reduction of silicon oxide through high activity during explosion, and the sintering is the preferred method step in order to make the reduction of silicon oxide more sufficient. The overall material preparation time can thereby be shortened.
Further, in order to obtain a cathode material with better performance, the material obtained by sintering can be subjected to carbon coating treatment after sintering, and the silicon-based cathode material doped with metal prepared by the invention can be obtained by hierarchical demagnetization.
The invention uses metal wire as conductor and siloxane gas as medium, and uses electric explosion method to make metal vapor and siloxane gas exchange heat, generate reduction reaction and deposit nucleation. The electric explosion method has rapid energy explosion, so the preparation time is short, the silicon crystal grain is controllable and the metal doping is uniform.
The particle size and the distribution of the particles can be effectively regulated and controlled by regulating the length and the diameter of the metal wire and the parameters of the high-energy electric pulse. In addition, the extreme conditions of the electric explosion method provide a thermodynamically unbalanced structure for the nano-metal particles and store excessive energy, so that the nano-metal particles obtained by explosion have high activity and can sufficiently reduce silicon oxide.
The application proposes that the diameter of the wire is 0.1-10 μm. Since the applicant found that when the diameter of the wire is more than 10 μm, the wire has a high density of electric explosion products, a supersaturated condition is easily achieved during the condensation of the explosion reaction, the particle growth time is long, and the particle diameter is large. The reduction of the diameter of the metal wire can effectively reduce the vapor density of the explosion reaction chamber, so that the particle size of the generated metal particles is reduced. And when the diameter of the wire is less than 0.1 μm, the installation of the wire is not easily accomplished.
The application proposes that the length of the wire is 10-200mm. Since the applicant found that when the length of the wire is less than 10mm, this results in a low doping level of the metal element, which is insufficient to completely reduce the silicon oxide formed by cracking. When the length of the metal wire is more than 200mm, the input energy consumption needs to be high in order to completely gasify the metal wire, and on the other hand, the doping content of the metal element is too high, so that the capacity and the first effect of the silicon-based material are influenced.
The application proposes that the high voltage capacitor has a voltage of 5kV-100kV. Since the applicant has found that the level of energy deposition is also an important factor affecting the metal particles. The magnitude of the capacitor voltage determines the amount of energy input to the wire. The energy deposition level is related to the sublimation energy of the wire in addition to the energy input to the wire. When the voltage of the capacitor is less than 5kV, the metal wire is in an underhot state at the moment, and the metal material can not be completely gasified. When the voltage of the capacitor is more than 100kV, the metal particles have narrow particle size distribution and smaller particle size, and the energy consumption is higher.
The present application proposes sintering temperatures of 600-1000 deg.C, such as 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C, 1000 deg.C or any temperature within the range. If the temperature is less than 600 ℃, the silica cannot be sufficiently reduced. If the temperature is higher than 1000 ℃, silicon crystallization is severe, and the size of silicon crystal grains is large, which affects the cycle performance of the material.
The present application contemplates sintering times in the range of 2 hours to 12 hours, such as 2 hours, 4 hours, 8 hours, 12 hours, or any time within the range. Sintering times of less than 2 hours can result in insufficient sintering. When the time is longer than 12 hours, the silicon crystal grains grow gradually and are easy to break in the circulating process, and the service life of the material is influenced.
The silicon-based negative electrode material prepared by the invention can be used as a negative electrode material active substance for a lithium battery negative electrode material and used for preparing a lithium battery negative electrode plate.
The negative electrode plate adopting the silicon-based negative electrode material further comprises a negative electrode current collector, the negative electrode current collector is not particularly limited as long as the purpose of the application can be achieved, and for example, the negative electrode plate can comprise but is not limited to a copper foil, a copper alloy foil, a nickel foil, a stainless steel foil, foamed nickel, foamed copper or a composite current collector and the like.
In the present application, the negative electrode material of the lithium battery may further include a conductive agent, and the conductive agent is not particularly limited in the present application, and any conductive agent commonly used in the art may be used as long as the purpose of the present application can be achieved.
The lithium battery adopting the silicon-based negative electrode material of the invention as the negative electrode material of the lithium battery can include but is not limited to: a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, a lithium ion polymer secondary battery, or the like.
The gram capacity of the negative active material of the silicon-based negative electrode material obtained by the preparation method is obviously improved, so that the lithium battery has higher energy density.
In order to better understand the technical solutions provided by the present invention, the following specific examples are respectively illustrated to describe the specific processes for preparing silicon-based materials by applying the methods provided by the above embodiments of the present invention, and the methods and characteristics for applying the same to lithium batteries.
Example 1
The electrode of the explosion reaction chamber was filled with a metal magnesium wire having a diameter of 2 μm and a length of 20mm. The explosion reaction chamber was evacuated and siloxane gas was introduced to 1 atmosphere. Charging the high-voltage capacitor to 30kV, switching on the gap gas switch, evaporating and exploding the metal wire under the action of pulse current, carrying out collision heat exchange on an explosion product and siloxane in an explosion reaction chamber, and forming a metal uniform doping material through a nucleation growth process.
Sintering the metal uniformly-doped material for 6 hours at 800 ℃ in a nitrogen atmosphere, and introducing a mixture of a metal oxide and a metal oxide with the volume ratio of 3:1, sintering the mixture at 900 ℃ for 1 hour to form carbon coating, and finally carrying out graded demagnetization to obtain the uniform metal-doped silicon-based negative electrode material.
The mass ratio of the silicon-based negative electrode material obtained in the above way as a negative electrode active material to carbon black as a conductive additive and an adhesive is 1:1, sodium carboxymethylcellulose and styrene butadiene rubber, in a mass ratio of 95%:2%:3% of the slurry is weighed and placed in a beater at room temperature for preparation of the slurry. And uniformly coating the prepared slurry on a copper foil. Drying in a forced air drying oven at 50 deg.C for 2 hr, cutting into 8 × 8mm pole pieces, and vacuum drying in a vacuum drying oven at 100 deg.C for 10 hr. And transferring the dried pole piece into a glove box for standby use to assemble a battery.
The simulated cell was assembled in a glove box containing a high purity Ar atmosphere using lithium metal as the counter electrode and 1 mole of LiPF 6 A dispersion in Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio v: v = 1:1) was used as an electrolyte to assemble a battery. The constant-current charge-discharge mode test is carried out by using a charge-discharge instrument, the discharge cutoff voltage is 0.005V, the charge cutoff voltage is 1.5V, the first-week charge-discharge test is carried out under the current density of C/10, and the second-week discharge test is carried out under the current density of C/10.
The gram capacity of the negative electrode material is 1420mAh/g, and the first efficiency is 87.0%.
Under the above conditions, the cycle test was performed, and the 50-week cycle capacity retention rate was 95%.
Example 2
The specific procedure is the same as in example 1. The difference is that the capacitor voltage is 45kV and the metal wire is an aluminum metal wire with a diameter of 5 μm and a length of 30mm.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1450mAh/g, and the first efficiency is 86.8%.
Under the above conditions, the cycle test was carried out, and the 50-week cycle capacity retention rate was 94%.
Example 3
The specific procedure was the same as in example 1. The difference is that the capacitor voltage is 60kV, the metal wire is magnesium metal wire with a diameter of 1.6 μm and a length of 60mm.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1398mAh/g, and the first efficiency is 87.3%.
Under the above conditions, the cycle test was carried out, and the 50-week cycle capacity retention rate was 94%.
Example 4
The specific procedure is the same as in example 1. The difference is that the capacitor voltage is 10kV, the metal wire is a magnesium metal wire with a diameter of 2.2 μm and a length of 20mm.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1411mAh/g, and the first efficiency is 86.9%.
Under the above conditions, a cycle test was performed, and the 50-week cycle capacity retention rate was 93%.
Example 5
The specific procedure was the same as in example 1. The difference is that the capacitor voltage is 55kV, the metal wire is a magnesium metal wire with a diameter of 5 μm and a length of 65mm.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1448mAh/g, and the first efficiency is 87.6%.
Under the above conditions, the cycle test was performed, and the 50-week cycle capacity retention rate was 92%.
Example 6
The specific procedure is the same as in example 1. The difference is that the capacitor voltage is 80kV, the metal wire is a copper metal wire with a diameter of 4 μm and a length of 80mm.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1460mAh/g, and the first efficiency is 87.0%.
Under the above conditions, a cycle test was carried out, and the 50-cycle capacity retention rate was 93%.
Example 7
The specific procedure was the same as in example 1. The difference is that the capacitor voltage is 30kV and the metal wire is an aluminum metal wire with a diameter of 3 μm and a length of 24mm.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1420mAh/g, and the first efficiency is 87.4%.
Under the above conditions, the cycle test was carried out, and the 50-week cycle capacity retention rate was 94%.
Example 8
The specific procedure was the same as in example 1. The difference is that the capacitor voltage is 48kV, the metal wire is a magnesium metal wire with a diameter of 4 μm and a length of 20mm.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1444mAh/g, and the first efficiency is 87.5%.
Under the above conditions, a cycle test was performed, and the 50-week cycle capacity retention rate was 93%.
The invention also provides comparative examples, which are intended to be compared with the examples given above.
Comparative example 1
The specific procedure was the same as in example 1. The difference is that the capacitor voltage is 2kV, the metal wire is a magnesium metal wire with a diameter of 2 μm and a length of 20mm.
Since the capacitor voltage is too low, the input energy is insufficient at this time to cause sublimation and vaporization of the metal wire, and thus a metal-doped silicon oxide material cannot be obtained.
Comparative example 2
The specific procedure was the same as in example 1. The difference is that the capacitor voltage is 30kV, the wire is magnesium wire with a diameter of 12 μm and a length of 20mm.
Because the diameter of the magnesium metal wire is too large, the resistance of the magnesium metal wire is too high, and the input energy is insufficient at the moment to cause the magnesium metal wire to sublimate and gasify, the magnesium-doped silica material cannot be obtained.
Comparative example 3
The specific procedure is the same as in example 1. The difference is that the capacitor voltage is 120kV, the metal wire is a magnesium metal wire with a diameter of 2 μm and a length of 20mm.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1384mAh/g, and the first efficiency is 85.4 percent.
Under the above conditions, a cycle test was carried out, and the 50-week cycle capacity retention rate was 68%.
Comparative example 4
Silicon oxide and silicon in a molar ratio of 1:1, and metal magnesium accounting for 10% of the total mass of the silicon and the silicon oxide are sintered for 6 hours at 1200 ℃ under a vacuum atmosphere of 50pa, and a silicon-oxygen composite material is formed on a substrate. Cooling the silica composite material to room temperature, discharging, crushing and screening; and (4) carrying out carbon coating on the crushed and sieved material to obtain the silicon-based lithium ion negative electrode material.
Cell assembly and cycling tests were performed according to the parameters and test conditions described above in example 1.
The gram capacity of the negative electrode material is 1340mAh/g, and the first efficiency is 85.3%.
Under the above conditions, a cycle test was carried out, and the 50-week cycle capacity retention rate was 85%.
From examples 1 to 8, it can be seen that the uniformly doped silica cathode material of different metal materials is successfully prepared by an electric explosion method by regulating and controlling the electrical parameters and the diameter and the length of the metal wire. Moreover, due to the advantages of the electric explosion method, the activity of the nano metal particles is high, and the silicon oxide can be fully reduced in the later reduction process, so that the efficiency is higher for the first time compared with the conventional commercial product. From comparative examples 1-2, the electric explosion process was not successful due to inappropriate selection of electrical and wire parameters. From comparative example 3, the prepared anode material has poor cycle performance due to excessively high voltage, excessively small nano metal particle size and excessively high activity. From comparative example 4, the magnesium-doped silica material prepared by the conventional method has low capacity and first-pass efficiency due to low reactivity.
The preparation method of the metal-doped silicon-based negative electrode material provided by the invention is characterized in that an electric explosion method is adopted to gasify a metal wire, and the metal wire is subjected to heat exchange with siloxane gas to generate cracking and reduction reactions, and nucleation and cooling are carried out to form the metal-uniformly-doped negative electrode material. The electric explosion method adopted by the invention has rapid energy explosion and short preparation time, and because the extreme condition of the electric explosion method provides a thermodynamic unbalanced structure for the nano metal particles and stores redundant energy, the nano metal particles obtained by explosion have high activity, silicon oxide can be fully reduced, the nucleated silicon crystal particles are controllable, and the metal elements are uniformly doped.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a metal-doped silicon-based anode material is characterized by comprising the following steps:
connecting a metal wire between two electrodes arranged in an explosion reaction chamber; one end electrode is connected to one end of the capacitor through the gap gas switch, and the other end electrode is connected to the other end of the capacitor;
vacuumizing the explosion reaction chamber, and introducing quantitative gaseous siloxane material;
the capacitor is charged, when the voltage at two ends of the capacitor exceeds the voltage critical value of the gap gas switch, the gap gas switch is switched on, high-energy electric pulses are generated through the discharge of the capacitor, the metal wires are evaporated and exploded to form nano metal particles, the nano metal particles collide with gaseous siloxane materials in the explosion reaction chamber for heat exchange, the siloxane materials are cracked to form silicon oxides, and the nano metal particles reduce the silicon oxides and grow through nucleation to form metal doped materials.
2. The method of preparing a metal-doped silicon-based anode material according to claim 1, further comprising:
and sintering the metal doped material in an inert gas atmosphere, performing carbon coating treatment on the sintered material, and removing magnetism in a grading manner to obtain the metal doped silicon-based negative electrode material.
3. The method for preparing the metal-doped silicon-based anode material according to claim 1, wherein the step of cracking the siloxane to form a silicon oxide specifically comprises:
the siloxane absorbs the heat energy released by the metal wire evaporation, and obtains the energy generated by the collision heat exchange between the nanometer metal particles and the siloxane in the explosion reaction chamber, and the nanometer metal particles are cracked to form silicon oxide.
4. The method for preparing a metal-doped silicon-based anode material according to claim 1, wherein the siloxane material specifically comprises siloxane and its derivatives;
the material of the metal wire comprises: one or more of magnesium, aluminum, lithium, sodium, titanium, zinc, iron, chromium, nickel, molybdenum, tin, germanium, calcium or copper; the diameter of the metal wire is 0.1-10 μm; the length is 10mm-200mm.
5. The method for preparing a metal-doped silicon-based anode material according to claim 1, wherein the capacitor is charged such that the voltage of the capacitor reaches 5kV-100kV.
6. The method for preparing the metal-doped silicon-based anode material according to claim 2, wherein the sintering temperature is 600-1000 ℃ and the sintering time is 2-12 hours.
7. A metal-doped silicon-based negative electrode material prepared by the method for preparing a silicon-based negative electrode material according to any one of claims 1 to 6.
8. A negative electrode material for a lithium battery, comprising the metal-doped silicon-based negative electrode material according to claim 7.
9. A lithium battery pole piece, characterized in that the lithium battery pole piece comprises the lithium battery negative electrode material of claim 8.
10. A lithium battery comprising a lithium battery electrode sheet according to claim 9.
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