CN114914418A - Silicon-based nano composite negative electrode material and preparation method thereof - Google Patents
Silicon-based nano composite negative electrode material and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 47
- 239000010703 silicon Substances 0.000 title claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013077 target material Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 230000003179 granulation Effects 0.000 claims abstract description 10
- 239000007921 spray Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 6
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- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 239000010405 anode material Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
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- 238000001816 cooling Methods 0.000 claims description 10
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 238000009768 microwave sintering Methods 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
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- 238000004544 sputter deposition Methods 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000002210 silicon-based material Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003749 cleanliness Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/386—Silicon or alloys based on silicon
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Abstract
The invention discloses a silicon-based nano composite negative electrode material and a preparation method thereof, relating to the technical field of lithium ion batteries, and the preparation method comprises the following steps: mixing and ball-milling graphene oxide, a binder, a dispersant and silicon nanoparticles in a protective atmosphere, and then adding deionized water into the mixed material to obtain slurry; spraying and granulating the slurry through a spray granulation tower to obtain powder; calcining the powder in a reducing atmosphere to obtain a silicon nano composite material coated with the redox graphene with a core-shell structure; and (3) coating the surface of the silicon nano composite material coated by the redox graphene by using Mg-doped ZnO as a target material and adopting a powder magnetron sputtering coating technology to obtain the silicon nano composite material. The silicon-based nano composite negative electrode material prepared by the invention not only can improve the rate capability and the electrical property, but also can inhibit the expansion of the nano silicon material, slow down the crushing of the nano silicon material and improve the cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-based nano composite negative electrode material and a preparation method thereof.
Background
At present, a plurality of automobile companies research electric automobiles, and the situation of the electric automobiles designed at present is that the time required for full charging is long, so that the requirements of people at present cannot be met. Most of the existing lithium ion battery cathode materials use traditional graphite materials, the theoretical capacity of the graphite materials is 372mAh/g, and the requirements of future development of electric automobiles cannot be met. Therefore, the development of the negative electrode material for the high-performance lithium ion battery, which has the advantages of fast charging, high energy density and long service life, is the key for the development of the electric automobile, and is also the key for realizing green environmental protection and relieving environmental pollution.
At present, the anode material of the battery in commerce is mainly graphite, the capacity of the graphite is almost increased to the limit, and the development of a higher and better novel battery anode material is the only way for meeting the market demand. Silicon is one of the best choices of the battery cathode at present, the theoretical specific capacity of the silicon material is high and reaches 4200mAh/g, the reaction activity with electrolyte is low, and the discharge platform is also low. However, silicon has a fatal disadvantage that silicon materials are crushed with volume change (up to 300%) during charge and discharge, and active materials are dropped from a current collector, and finally, capacity is sharply reduced, thereby preventing the development of a silicon negative electrode. The method of coating the silicon material to suppress the volume expansion and pulverization thereof is very effective. The conductivity of the silicon material is lower by several orders of magnitude compared with that of a graphite material, and when the silicon material is coated, some materials with better conductivity need to be selected for coating the silicon material.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a silicon-based nano composite anode material and a preparation method thereof.
The invention provides a preparation method of a silicon-based nano composite anode material, which comprises the following steps:
s1, mixing and ball-milling the graphene oxide, the binder, the dispersant and the silicon nanoparticles in a protective atmosphere, and then adding deionized water into the mixed materials to obtain slurry;
s2, performing spray granulation on the slurry through a spray granulation tower to obtain powder;
s3, calcining the powder in a reducing atmosphere to obtain the silicon nano composite material coated with the redox graphene with the core-shell structure;
and S4, coating the surface of the silicon nano composite material coated by the redox graphene by using Mg-doped ZnO as a target material and adopting a powder magnetron sputtering coating technology to obtain the silicon-based nano composite negative electrode material coated by both Mg-doped ZnO and redox graphene.
Preferably, in S1, the mass ratio of the graphene oxide, the binder, the dispersant, and the silicon nanoparticles is 2: 2-3: 2-3: 18; wherein the graphene oxide is prepared by a Hummers method; the binder is styrene butadiene rubber or polyacrylic acid; the dispersant is sodium carboxymethyl cellulose.
The binder is styrene butadiene rubber or polyacrylic acid, wherein the styrene butadiene rubber is a water-based binder and a coexisting substance of hydrophilicity and lipophilicity, a water-based group is combined with a foil surface group to form a binding power, the dispersibility and the slurry stability are facilitated, and an oil chain segment is combined with negative electrode graphite to form the binding power, so that the binding effect is achieved; polyacrylic acid is a water-soluble chain polymer, can form polyacrylate with a plurality of metal ions, can form hydrogen bond action with the surface of a silicon-carbon active material, endows stronger binding force between active particles and a current collector, and can relieve the volume expansion action of a silicon-based material, and is mainly used as a binder to improve the stability of slurry.
The dispersant is sodium carboxymethyl cellulose (CMC), is an ionic linear high molecular substance, is easily dissolved in cold water, hot water and polar solvent to form transparent viscous liquid, and can be added during the preparation of electrode slurry to improve the viscosity of the slurry and prevent the precipitation of the slurry.
Preferably, in S1, the ball milling is carried out for 4-10h, and the ball milling rotation speed is 200-500 r/min.
Preferably, in S1, deionized water is added to adjust the viscosity of the slurry at 3000-5000Pa · S.
Preferably, in S2, the process parameters of spray granulation are: the feeding speed of the slurry is 50-100kg/h, the inlet air temperature is 230-; obtaining solid powder with particle size D50 of 10-13 μm and tap density of 1.3-1.4cm 3 /g。
Preferably, in S3, the powder is calcined in a reducing atmosphere of mixed gas of nitrogen and hydrogen by microwave at 400-500 ℃ for 15-30min in a microwave sintering furnace; wherein the volume ratio of nitrogen to hydrogen in the mixed gas is 100: 5-10.
Preferably, the specific operation of microwave calcination is as follows: heating to 300 deg.C at a heating rate of 2 deg.C/min, and maintaining for 5 min; then heating to 400-450 ℃ at a heating rate of 1.5 ℃/min, calcining for 15-30min, and finally cooling to room temperature at a cooling rate of 1.5 ℃/min.
Preferably, in S4, the process parameters of the powder magnetron sputtering coating are as follows: the sputtering power is 1-5w/cm 2 The cathode power supply adopts a constant current mode, the current is 30-45A, the deposition voltage is 350-450V, and the time is 2-10 min.
Preferably, in S4, the thickness of the coating film is controlled to be 100-180 nm.
The invention also provides the silicon-based nano composite anode material prepared by the method.
Has the advantages that: according to the invention, the nano silicon material is coated by the redox graphene, so that the volume expansion of the nano silicon material as the lithium ion battery cathode material in the circulation process is inhibited, the crushing of the nano silicon material is slowed down, and the circulation performance is improved; and then, coating the silicon anode material by adopting Mg-doped ZnO, further increasing the coating uniformity and conductivity, improving the electronic conductivity of the silicon anode material and increasing the rate capability of the silicon anode material.
Drawings
Fig. 1 is an SEM image of a silicon-based nanocomposite negative electrode material prepared in example 3 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a silicon-based nano composite anode material comprises the following steps:
s1, mixing graphene oxide prepared by a Hummers method, styrene butadiene rubber, sodium carboxymethyl cellulose and silicon nanoparticles with the particle size of 80nm according to a mass ratio of 2: 2: 3: 18, adding the mixture into a ball mill, introducing an argon/nitrogen (ratio is 1:1) inert atmosphere, carrying out ball milling for 5 hours under the protection of the argon/nitrogen inert atmosphere, wherein the ball milling rotation speed is 300r/min, adding the mixture into a vacuum stirrer after the ball milling is finished, injecting deionized water into the stirrer, stirring for 2 hours at the stirring rotation speed of 500r/min, and adjusting the viscosity to 3800Pa & S to obtain a slurry with uniform and good dispersion;
s2, filtering the slurry by using a 200-mesh drying net, adding the obtained uniformly dispersed slurry into a feeding barrel, feeding the slurry into a spray granulation tower through a peristaltic pump, wherein the feeding speed is controlled at 60kg/h, the air inlet temperature is controlled at 238 ℃, the air outlet temperature is controlled at 113 ℃, the rotating speed of an atomizing disc is controlled at 13500r/min, the negative pressure in the tower is 0.1MPa, the particle size D50 of the solid powder is 11 mu m, and the tap density is 1.35cm 3 /g；
S3, sieving the obtained powder particles with a 200-mesh sieve, putting the powder particles into a graphite crucible, putting the graphite crucible into a microwave sintering furnace protected by nitrogen/hydrogen reducing atmosphere (volume ratio is 100: 5), heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 5min, heating to 450 ℃ at 1.5 ℃/min, calcining for 15min, and cooling to room temperature at a cooling rate of 1.5 ℃/min to obtain the silicon nanocomposite coated with the redox graphene with the core-shell structure;
s4, taking Mg-doped ZnO as a target material, putting the silicon nano composite material coated by the redox graphene into a process cavity of coating equipment, vacuumizing the process cavity, and ensuring that the requirement of the background vacuum degree is superior to 5 multiplied by 10 - 4 Pa; re-introducing process gas (nitrogen) into the process cavity to maintain the pressure in the process cavity at 0.3Pa, and coating the powder with coating power of 1W/cm at the conditions of air cleanliness up to ten thousand, humidity below 50%, and temperature of 20 deg.C 2 The cathode power supply adopts a constant current mode, the current is 40A, the deposition voltage is 300V, the Mg-doped ZnO target material is uniformly coated on the surface of the composite material by a powder surface coating technology, and the thickness of the Mg-doped ZnO film layer is controlled to be 130nm, so that the silicon-based nano composite cathode material jointly coated by the redox graphene and the Mg-doped ZnO is obtained.
Example 2
A preparation method of a silicon-based nano composite anode material comprises the following steps:
s1, mixing graphene oxide prepared by a Hummers method, polyacrylic acid, sodium carboxymethyl cellulose and silicon nanoparticles with the particle size of 60nm according to a mass ratio of 2: 3: 2: 18, adding the mixture into a ball mill, introducing an inert atmosphere of argon/nitrogen (the ratio is 1:1), carrying out ball milling for 6 hours under the protection of the inert atmosphere of argon/nitrogen, wherein the ball milling rotating speed is 400r/min, adding the mixture into a vacuum stirrer after the ball milling is finished, injecting deionized water into the stirrer, stirring for 2 hours at the stirring rotating speed of 500r/min, and adjusting the viscosity to 4000 Pa.S, so as to obtain a slurry with uniform and good dispersion;
s2, filtering the slurry with a 200-mesh drying net, adding the obtained uniformly dispersed slurry into a feeding barrel, feeding into a spray granulation tower through a peristaltic pump, wherein the feeding speed is controlled at 50kg/h of slurry, and the air inlet temperature is controlled atThe temperature is controlled at 230 ℃, the temperature of an air outlet is controlled at 115 ℃, the rotating speed of an atomizing disc is controlled at 12000r/min, the negative pressure in the tower is 0.2MPa, the particle size D50 of the solid powder is 13 mu m, and the tap density is 1.3cm 3 /g；
S3, sieving the obtained powder particles with a 200-mesh sieve, putting the powder particles into a graphite crucible, putting the graphite crucible into a microwave sintering furnace protected by nitrogen/hydrogen reducing atmosphere (volume ratio is 100: 10), heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 5min, heating to 400 ℃ at 1.5 ℃/min, calcining for 15min, and cooling to room temperature at a cooling rate of 1.5 ℃/min to obtain the silicon nanocomposite coated with the redox graphene with the core-shell structure;
s4, taking Mg-doped ZnO as a target material, putting the target material with the purity of more than 3N into a process cavity of coating equipment, vacuumizing the process cavity, and ensuring that the requirement of the background vacuum degree is superior to 5 multiplied by 10 -4 Pa; re-introducing process gas (nitrogen) into the process cavity to maintain the pressure in the process cavity at 0.1Pa, and coating the powder with coating power of 1W/cm at the temperature of 17 deg.C and humidity below 50% and air cleanliness of ten thousand grade 2 The cathode power supply adopts a constant current mode, the current is 30A, the deposition voltage is 350V, the Mg-doped ZnO target material is uniformly coated on the surface of the composite material by a powder surface coating technology, and the thickness of the Mg-doped ZnO film layer is finally 150nm, so that the silicon-based nano composite cathode material jointly coated by the redox graphene and the Mg-doped ZnO is obtained.
Example 3
A preparation method of a silicon-based nano composite anode material comprises the following steps:
s1, mixing graphene oxide prepared by a Hummers method, styrene butadiene rubber, sodium carboxymethyl cellulose and silicon nanoparticles with the particle size of 60nm according to a mass ratio of 2: 2: 3: 18, adding the mixture into a ball mill, introducing argon/nitrogen (the ratio is 1:1) inert atmosphere, carrying out ball milling for 10 hours under the protection of the argon/nitrogen inert atmosphere, wherein the ball milling rotation speed is 500r/min, adding the mixture into a vacuum stirrer after the ball milling is finished, injecting deionized water into the stirrer, stirring for 2 hours, wherein the stirring rotation speed is 800r/min, and adjusting the viscosity to be 5000 Pa.S, so as to obtain a slurry with uniform and good dispersion;
s2, filtering the slurry by using a 200-mesh drying net, adding the obtained uniformly dispersed slurry into a feed barrel, feeding the slurry into a spray granulation tower through a peristaltic pump, wherein the feeding speed is controlled at 80kg/h, the air inlet temperature is controlled at 245 ℃, the air outlet temperature is controlled at 110 ℃, the rotating speed of an atomizing disc is controlled at 12000r/min, the negative pressure in the tower is 0.3MPa, the particle size D50 of the solid powder is 11 mu m, and the tap density is 1.40cm 3 /g；
S3, sieving the obtained powder particles with a 200-mesh sieve, putting the powder particles into a graphite crucible, putting the graphite crucible into a microwave sintering furnace protected by nitrogen/hydrogen reducing atmosphere (volume ratio is 100: 8), heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 5min, heating to 450 ℃ at 1.5 ℃/min, calcining for 15min, and cooling to room temperature at a cooling rate of 1.5 ℃/min to obtain the silicon nanocomposite coated with the redox graphene with the core-shell structure;
s4, taking Mg-doped ZnO as a target material, putting the target material with the purity of more than 3N into a process cavity of coating equipment, vacuumizing the process cavity, and ensuring that the requirement of the background vacuum degree is superior to 5 multiplied by 10 -4 Pa; re-introducing process gas (nitrogen) into the process cavity to maintain the pressure in the process cavity at 0.5Pa, and performing sputtering coating on the powder by starting a cathode power supply of a coating device under the conditions of humidity below 50% and temperature of 20 ℃ and air cleanliness of ten thousand levels in the coating environment, wherein the coating power is 3W/cm 2 The cathode power supply adopts a constant current mode, the current is 50A, the deposition voltage is 350V, the Mg-doped ZnO target material is uniformly coated on the surface of the composite material by a powder surface coating technology, and the thickness of the Mg-doped ZnO film layer is finally 110nm, so that the silicon-based nano composite cathode material jointly coated by the redox graphene and the Mg-doped ZnO is obtained.
Comparative example
Compared with the embodiment 3, the preparation method of the silicon-based nano composite anode material only has the following differences: the step of S4 is not included.
The silicon-based nanocomposite negative electrode materials prepared in examples 1 to 3 of the present invention and comparative example were subjected to performance testing, and the results are shown in table 1 and fig. 1.
TABLE 1 cyclability data for examples 1-3 and comparative examples
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Gram volume | 1400mAh/g | 1250mAh/g | 1500mAh/g | 1650mAh/g |
| First effect | 89.5％ | 88.7％ | 90.0％ | 90.5％ |
| Full power rebound | 68％ | 60％ | 73％ | 80％ |
| Normal temperature cycle performance | 80% at 850 weeks | 980 weeks @ 80% | 750 weeks @ 80% | @ 80% in 600 weeks |
As can be seen from Table 1, the gram capacity of the material is reduced, the first effect is reduced, the rebound is reduced correspondingly as the coating amount is increased, and the cycle performance is further improved.
Fig. 1 is an SEM image of a silicon-based nanocomposite negative electrode material prepared in example 3, and it can be seen from the SEM image that the coating layer deposited on the surface is relatively uniform after two coating processes, and the improvement of uniformity can suppress the bouncing in view of the data of the example.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The preparation method of the silicon-based nano composite anode material is characterized by comprising the following steps of:
s1, mixing and ball-milling the graphene oxide, the binder, the dispersant and the silicon nanoparticles in a protective atmosphere, and then adding deionized water into the mixed materials to obtain slurry;
s2, performing spray granulation on the slurry through a spray granulation tower to obtain powder;
s3, calcining the powder in a reducing atmosphere to obtain a silicon nano composite material coated by redox graphene with a core-shell structure;
and S4, coating the surface of the silicon nano composite material coated by the redox graphene by using Mg-doped ZnO as a target material and adopting a powder magnetron sputtering coating technology to obtain the silicon-based nano composite negative electrode material coated by both Mg-doped ZnO and redox graphene.
2. The method for preparing the silicon-based nano composite anode material according to claim 1, wherein in S1, the mass ratio of the graphene oxide to the binder to the dispersing agent to the silicon nanoparticles is 2: 2-3: 2-3: 18; wherein the graphene oxide is prepared by a Hummers method; the binder is styrene butadiene rubber or polyacrylic acid; the dispersant is sodium carboxymethyl cellulose.
3. The preparation method of the silicon-based nanocomposite anode material as claimed in claim 1, wherein in S1, the ball milling is performed for 4-10h at a rotation speed of 200-500 r/min.
4. The method for preparing the silicon-based nano composite anode material as claimed in claim 1, wherein deionized water is added into S1 to adjust the viscosity of the slurry to 3000-5000 Pa.S.
5. The method for preparing the silicon-based nano composite anode material according to claim 1, wherein in S2, the technological parameters of spray granulation are as follows: the feeding speed of the slurry is 50-100kg/h, the inlet air temperature is 230-; obtaining solid powder with particle size D50 of 10-13 μm and tap density of 1.3-1.4cm 3 /g。
6. The method for preparing the silicon-based nano composite anode material as claimed in claim 1, wherein in S3, the powder is calcined in a reducing atmosphere of a mixed gas of nitrogen and hydrogen by microwave at 400-500 ℃ for 15-30min in a microwave sintering furnace; wherein the volume ratio of nitrogen to hydrogen in the mixed gas is 100: 5-10.
7. The preparation method of the silicon-based nanocomposite anode material according to claim 6, wherein the microwave calcination is specifically performed by: heating to 300 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 5 min; then heating to 400-450 ℃ at a heating rate of 1.5 ℃/min, calcining for 15-30min, and finally cooling to room temperature at a cooling rate of 1.5 ℃/min.
8. The method for preparing the silicon-based nano composite anode material according to claim 1, wherein in S4, the technological parameters of the powder magnetron sputtering coating are as follows: the sputtering power is 1-5w/cm 2 The cathode power supply adopts a constant current mode, the current is 30-45A, the deposition voltage is 350-450V, and the time is 2-10 min.
9. The method for preparing the silicon-based nanocomposite negative electrode material as recited in claim 1, wherein in S4, the thickness of the coating film is controlled to be 100-180 nm.
10. A silicon-based nanocomposite anode material prepared according to the method of any of claims 1 to 9.
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