CN109585829A - A kind of silicon based anode material and its preparation method and application - Google Patents

A kind of silicon based anode material and its preparation method and application Download PDF

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Publication number
CN109585829A
CN109585829A CN201811464722.7A CN201811464722A CN109585829A CN 109585829 A CN109585829 A CN 109585829A CN 201811464722 A CN201811464722 A CN 201811464722A CN 109585829 A CN109585829 A CN 109585829A
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silicon
preparation
based anode
anode material
silicon based
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牛丽媛
郑东
沈长海
刘慧军
金源
谢健
郭永斌
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Zhejiang Zhongtai Automobile Manufacturing Co Ltd
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Zhejiang Zhongtai Automobile Manufacturing Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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 kind of silicon based anode materials and its preparation method and application, specially, the material of the silicon oxide-containing of business is first subjected to high temperature sintering and pickling obtains silica, it reacts silica progress metallothermic reduction to obtain porous nano silicon, silicon substrate composite negative pole material is obtained in nanometer silicon face coated polymer by in-situ polymerization again.Compared with prior art, the advantages that present invention uses the material of cheap silicon oxide-containing for presoma, prepares nano-silicon using metal thermal response, has energy consumption low, and cost is small, and the period is short, is conducive to large-scale production.The present invention uses the polymer overmold porous nano silicon of in-situ polymerization, prepares silicon/polymer composite negative pole material with high capacity and excellent cycle performance.

Description

A kind of silicon based anode material and its preparation method and application
Technical field
The present invention relates to the technical fields of energy-storage battery, and in particular to a kind of silicon based anode material and preparation method thereof and answers With.
Background technique
Lithium ion battery is widely used as mobile electronic device, such as smart phone, laptop now, and in electricity Net energy storage, electric car field have huge market.But with lithium ion battery on electric car large-scale use, Traditional graphite-based cathode is not able to satisfy the requirement of the growing high-energy density of power battery.Relative to graphite-based cathode, silicon The theoretical capacity of base cathode reaches 4200mAh/g, with important application prospects.
But during forming Li-Si alloy, volume expansion is up to 300%, has seriously affected the cycle life of material. Currently, improve silicium cathode cycle life measure mainly have: with carbon material it is compound, silicon particle size is down to nanoscale, formed Porous structure.Although the cycle performance of silicon-based anode can be improved in nanosizing, Composite, the letter of nano silica-base material is realized Single, prepare with scale still faces very big challenge.In addition, being different from graphite cathode, silicon-based anode is hardly formed stable SEI film, Remaining HF also has corrosiveness to silicon in electrolyte, needs to carry out silicon certain surface protection, forms artificial SEI film.
Summary of the invention
The present invention provides a kind of silicon based anode materials, and the silicon based anode material is by porous nano silicon particle and disperse in hole In polymer composition, by the way that the chemical property of silica-base material can be effectively improved by silicon nanosizing and compound with polymer, Special coulombic efficiency and cyclical stability for the first time.
The present invention also provides a kind of preparation method of silicon based anode material, the commercial materials with cheap silicon oxide-containing are Presoma obtains porous nano-silicon by simple metallothermic reduction, and the volume change during metallothermic reduction can will be micro- Meter level silica is transformed into nanoscale silicon particle, then is infiltrated by simple liquid phase and situ aggregation method, obtain nano-silicon/ Polymer composites.Using the protective effect of polymer, the stability of silicon-based anode is improved.
A kind of application the present invention also provides silicon based anode material as battery material.
Specific technical solution of the present invention is as follows:
A kind of silicon based anode material, the silicon based anode material by porous nano silicon particle and disperse Yu Kongzhong polymer Composition.
The polymer is selected from polymerized thylene carbonate vinyl acetate.
Preferably, by weight percentage, polymer is the 5%~25% of porous nano silicon particle, further preferably, poly- carbon Sour vinylene is the 5%-10% of porous nano silicon particle.Within this range, be conducive to polymer and coat silicon particle completely, Effective protective film is formed, and does not hinder the diffusion of lithium ion.
Preferably, the size of the porous nano silicon particle is 10nm~500nm, further preferably, the porous nano The size of silicon particle is 50nm~200nm.Too small particle is unfavorable for the uniform cladding of solid electrolyte, and too small particle is also easy By electrolytic corrosion, excessive particle is unfavorable for the diffusion of lithium ion.
In lithium ion battery, vinylene carbonate is used as film forming agent, in vinylene carbonate ester structure due to Containing carbon-carbon double bond, by adding vinylene carbonate in the electrolytic solution, vinylene carbonate can in charge and discharge process for battery Polymerization reaction occurs, protective film is formed in electrode surface, inhibits electrolyte in the side reaction of electrode surface.The present invention is by poly- carbon Sour vinylene is infiltrated into the gap of porous silicon, by in-situ polymerization, nano-silicon and polymer it is compound more uniform.Pass through Polymerized thylene carbonate vinyl acetate is introduced, on the one hand can buffer volume change of the silicon in charge and discharge process, and can inhibit silicon nanoparticle Reunion fine and close polymeric protective film on the other hand can be formed on silicon particle surface, inhibit connecing for silicon particle and electrolyte Touching, to prevent corrosion of the silicon by electrolyte, improves the cyclical stability of material.
A kind of preparation method of silicon based anode material provided by the invention, comprising the following steps:
1) by after the raw material high-temperature heat treatment of silicon oxide-containing, pickling obtains pure silica；
2) pure silica obtained in step 1) is uniform through ball milling mixing with reducing metal and metal chloride；
3) mixture obtained by step 2) is placed in atmosphere protection stove, is passed through inert gas, carry out metallothermic reduction reaction, It is cooled to room temperature, obtains metallothermic reduction product；
4) metallothermic reduction product obtained by step 3) is obtained into porous nano silicon after pickling, dry；
5) porous nano silicon obtained by step 4) is uniformly mixed with polymer monomer, initiator is added and carries out in-situ polymerization, Obtain silicon based anode material.
The raw material of silicon oxide-containing described in step 1) using it is cheap, be easy to get, preferably diatomite, kaolin, quartz sand Or diopside.
High-temperature heat treatment described in step 1) refers in air atmosphere, processing 1 under the conditions of temperature is 600~1000 DEG C~ 5 hours.
Pickling described in step 1) refers to is cleaned using the hydrochloric acid or sulfuric acid of 1~10mol/L of concentration, the time be 5~ 24 hours.
Step 1) first carries out high-temperature heat treatment to raw material under air atmosphere, can remove the organic matter in presoma and other are waved Hair point.Then, pickling is carried out to high-temperature process product, by cleaning, iron oxide, aluminium oxide, sodium oxide molybdena, titanium oxide etc. can be removed Impurity.By high-temperature process and pickling, purer siliconoxide precursor can be obtained.
In step 2), the reducing metal is magnesium metal, metallic aluminium or metallic zinc.
Further, in step 2) preferably, the molar ratio of the magnesium metal or metallic zinc and pure silica be 2~ 2.1:1；The molar ratio of the metallic aluminium and pure silica is 4.0~4.3:3.
Further, the weight ratio of metal chloride described in step 2) and silica is 5~10:1.The metal chlorination Object is the one or more of sodium chloride, potassium chloride, magnesium chloride, zinc chloride or aluminium chloride.
Ball milling described in step 2) refers under the conditions of revolving speed 180r/min ball milling 10 hours.
By the dosage of optimization reducing metal and metal chloride in step 2), going back completely for silica is on the one hand realized Original obtains of uniform size, well dispersed silicon nanoparticle, and can reduce the cost of preparation.
The reaction of metallothermic reduction described in step 3) refers to reacts 2~20 hours under the conditions of temperature is 500~900 DEG C；It is excellent Choosing, the metallothermic reduction reaction refers to reacts 5~15 hours under the conditions of temperature is 750~850 DEG C.
Step 3) can both realize the complete reduction by silica by optimization metal fever reaction temperature and time, improve and produce Rate avoids the cleaning of subsequent oxidation silicon, and can reduce the reunion of silicon nanoparticle.
Pickling described in step 4) refers to is cleaned using the hydrochloric acid or sulfuric acid of 1~10mol/L of concentration, the time be 5~ 24 hours.
In-situ polymerization described in step 5) reacts 5~30 hours under the conditions of temperature is 50~90 DEG C；Preferably, the original Position, which is aggregated under the conditions of temperature is 60~80 DEG C, reacts 5~10 hours.
Polymer monomer described in step 5) is selected from ethylene carbonate.
In step 5), by weight percentage, polymerized thylene carbonate vinyl acetate is the 5%~25% of porous nano silicon particle, into one Preferably, polymerized thylene carbonate vinyl acetate is the 5%-10% of porous nano silicon particle to step.
Initiator described in step 5) is azo-initiator, including azodiisobutyronitrile, azobisisoheptonitrile or azo Two isobutyl dimethyl phthalates.
Further, the dosage of initiator described in step 5) are as follows: every milliliter of vinylene carbonate is added 0.5~2 milligram Initiator.
Step 5) obtains polymerized thylene carbonate vinyl acetate using the method for in-situ polymerization, and by infiltration to the gap of porous silicon In, by in-situ polymerization, nano-silicon and polymer it is compound more uniform.By introducing polymerized thylene carbonate vinyl acetate, on the one hand may be used Volume change of the silicon in charge and discharge process is buffered, and can inhibit the reunion of silicon nanoparticle, it on the other hand, can be in silicon particle table Face forms fine and close polymeric protective film, and contact of the silicon particle with electrolyte is inhibited to mention to prevent corrosion of the silicon by electrolyte The cyclical stability of high material.
Application the present invention also provides a kind of silicon based anode material using above method preparation as battery material.It can The chemical property of silica-base material is effectively improved, especially coulombic efficiency and cyclical stability for the first time.
A kind of letter is provided for prepare with scale nano-silicon by reacting silica progress metallothermic reduction for nano-silicon Folk prescription method can realize the crushing of feed particles by the stress of the volume change of metallothermic reduction reaction process, to obtain more Hole nano-silicon can not only prevent the reunion of silicon particle, but also can be in silicon nanoparticle surface shape by further compound with polymer At artificial SEI film, the contact with electrolyte is reduced to reduce the generation of side reaction.
Compared with prior art, the present invention uses the material of cheap silicon oxide-containing for presoma, using metal thermal response Nano-silicon is prepared, there is low, the advantages that cost is small, and the period is short of consuming energy, be conducive to large-scale production.The present invention uses in-situ polymerization Polymer overmold porous nano silicon, prepare silicon/polymer composite negative pole material, can both buffer silicon in lithiumation/de- lithiumation process In volume change, and contact of the silicon particle with electrolyte can be prevented to inhibiting silicon by electrolytic corrosion, but do not influence lithium from Diffusion of the son from liquid electrolyte to silicon particle.The chemical property of silica-base material can be effectively improved, especially coulombic efficiency for the first time And cyclical stability.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of silicon based anode material prepared by embodiment 1；
Fig. 2 is scanning electron microscope (SEM) photo of silicon based anode material prepared by embodiment 1；
Fig. 3 is using silicon based anode material prepared by embodiment 1 as the charging and discharging curve of negative electrode of lithium ion battery.
Specific embodiment
Embodiment 1
A kind of preparation method of silicon based anode material, comprising the following steps:
1) first by calcination 2 hours under the conditions of diatomite in air 800 DEG C, then firing product is clear with the hydrochloric acid of 6mol/L It washes 12 hours, is washed with deionized to neutrality, obtains pure silica；
2) by the pure silica of step 1) preparation and magnesium powder and sodium chloride through ball milling mixing, rotational speed of ball-mill 180r/min, Ball-milling Time is 10 hours, obtains mixture；The molar ratio of magnesium powder and pure silica is 2:1, the weight of sodium chloride and pure silica Amount is than being 6:1；
3) mixture prepared by step 2) is placed in tube furnace, is passed through argon gas, carry out magnesiothermic reduction reaction, reaction temperature It is 800 DEG C, the reaction time is 10 hours；Obtain magnesium thermit product；
4) the magnesium thermit product by step 3) preparation cleans 12 hours through 1mol/L hydrochloric acid, is washed with deionized into Property, porous nano silicon is obtained after dry；
5) porous nano silicon obtained by step 4) is immersed into vinylene carbonate, porous nano silicon and vinylene carbonate Weight ratio be 10:1, be added initiator azobisisoheptonitrile, 0.5 milligram of azo two different heptan is added in every milliliter of vinylene carbonate Then nitrile carries out in-situ polymerization 10 hours at 60 DEG C, obtains silicon/vinylene carbonate composite material, i.e. silicon based anode material.
Product silicon based anode material prepared by embodiment 1 is detected as the silicon of pure phase through XRD, and polymer is due to being presented amorphous State does not occur in diffraction maximum, sees Fig. 1.Thermogravimetric analysis shows product weightlessness about 9%, it was demonstrated that has the presence of polymer, contains Amount about 9%.SEM shows that nano-silicon primary particle is 50~200nm, and surface is coated with uniform polymeric layer, sees Fig. 2.
A kind of application of silicon based anode material as battery material, specifically:
Using silicon based composite material manufactured in the present embodiment as anode, using lithium metal as cathode, Celgard2325 film be every Film, LiPF6Ethylene carbonate (EC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) solution (volume ratio 1:1:1) be Electrolyte assembles battery in the glove box full of argon gas, carries out charge-discharge test, and charging and discharging curve is as shown in Figure 3.Constant current Charge-discharge test (current density 100mA/g, 0.005~2.5V of voltage range), from figure it is found that discharge capacity is up to 2854mAh/ G, coulombic efficiency is 83% for the first time.
Comparative example 1
The preparation of nano silica-base material such as embodiment 1, difference are that the temperature of step 3) magnesium thermit is 450 DEG C, instead It is 10 hours between seasonable.At this point, still there is more silica in product, discharge capacity is lower than 800mAh/g, coulombic efficiency for the first time Lower than 50%.
Comparative example 2
The preparation of nano silica-base material such as embodiment 1, difference are that the temperature of step 3) magnesium thermit is 800 DEG C, instead It is 1.5 hours between seasonable.At this point, still there is more silica in product, discharge capacity is lower than 2000mAh/g, coulomb effect for the first time Rate is lower than 75%.
Comparative example 3
The preparation of nano silica-base material such as embodiment 1, difference are (not carry out step 5) without introducing polymer. At this point, discharge capacity is lower than 2900mAh/g for the first time, coulombic efficiency is lower than 75%.
Comparative example 4
The preparation of nano silica-base material such as embodiment 1, difference are that sodium chloride is not added for step 2), and step 3) magnesium heat is anti- Seasonable no introducing sodium chloride.At this point, particle agglomeration, than more serious, discharge capacity is lower than 2800mAh/g for the first time, coulombic efficiency is low In 80%.
Embodiment 2
A kind of preparation method of silicon based anode material, comprising the following steps:
1) first by calcination 2 hours under the conditions of kaolin in air 800 DEG C, then firing product is clear with the hydrochloric acid of 6mol/L It washes 12 hours, is washed with deionized to neutrality, obtains pure silica；
2) by the pure silica of step 1) preparation and aluminium powder and potassium chloride through ball milling mixing, rotational speed of ball-mill 180r/min, Ball-milling Time is 10 hours, obtains mixture；The molar ratio of aluminium powder and pure silica is 4.0:3, potassium chloride and pure silica Weight ratio is 7:1；
3) mixture prepared by step 2) is placed in tube furnace, is passed through argon gas, carry out magnesiothermic reduction reaction, reaction temperature It is 850 DEG C, the reaction time is 5 hours；Obtain magnesium thermit product；
4) the magnesium thermit product by step 3) preparation cleans 12 hours through 1mol/L hydrochloric acid, is washed with deionized into Property, porous nano silicon is obtained after dry；
5) porous nano silicon obtained by step 4) is immersed into vinylene carbonate, porous nano silicon and vinylene carbonate Weight ratio be 7:1, be added initiator azobisisoheptonitrile, 0.5 milligram of azo two different heptan is added in every milliliter of vinylene carbonate Then nitrile carries out in-situ polymerization 10 hours at 60 DEG C, obtains silicon/vinylene carbonate composite material, i.e. silicon based anode material.
Product is detected as the silicon of pure phase through XRD, and polymer is due to being presented amorphous state.SEM shows nano-silicon primary Grain is 50~200nm, and surface is coated with uniform polymeric layer.
A kind of application of silicon based anode material as battery material, specifically:
Using silicon based composite material manufactured in the present embodiment as anode, using lithium metal as cathode, Celgard2325 film be every Film, LiPF6EC/DEC/DMC solution (volume ratio 1:1:1) be electrolyte, full of argon gas glove box in assemble battery, Carry out charge-discharge test.Constant current charge-discharge test (current density 100mA/g, 0.005~2.5V of voltage range) shows electric discharge Capacity is up to 2900mAh/g, and coulombic efficiency is 81% for the first time.
Embodiment 3
A kind of preparation method of silicon based anode material, comprising the following steps:
1) first by calcination 2 hours under the conditions of quartz sand in air 800 DEG C, then firing product is clear with the hydrochloric acid of 6mol/L It washes 12 hours, is washed with deionized to neutrality, obtains pure silica；
2) by the pure silica of step 1) preparation and magnesium powder and magnesium chloride through ball milling mixing, rotational speed of ball-mill 180r/min, Ball-milling Time is 10 hours, obtains mixture；The molar ratio of magnesium powder and pure silica is 2.1:1, magnesium chloride and pure silica Weight ratio is 9:1；
3) mixture prepared by step 2) is placed in tube furnace, is passed through argon gas, carry out magnesiothermic reduction reaction, reaction temperature It is 750 DEG C, the reaction time is 15 hours；Obtain magnesium thermit product；
4) the magnesium thermit product by step 3) preparation cleans 12 hours through 1mol/L hydrochloric acid, is washed with deionized into Property, porous nano silicon is obtained after dry；
5) porous nano silicon obtained by step 4) is immersed into vinylene carbonate, porous nano silicon and vinylene carbonate Weight ratio be 5:1, be added initiator azobisisoheptonitrile, 0.5 milligram of azo two different heptan is added in every milliliter of vinylene carbonate Then nitrile carries out in-situ polymerization 10 hours at 60 DEG C, obtains silicon/vinylene carbonate composite material, i.e. silicon based anode material.
Product is detected as the silicon of pure phase through XRD, and polymer is due to being presented amorphous state.SEM shows nano-silicon primary Grain is 50~200nm, and surface is coated with uniform polymeric layer.
A kind of application of silicon based anode material as battery material, specifically:
Using silicon based composite material manufactured in the present embodiment as anode, using lithium metal as cathode, Celgard2325 film be every Film, LiPF6EC/DEC/DMC solution (volume ratio 1:1:1) be electrolyte, full of argon gas glove box in assemble battery, Carry out charge-discharge test.Constant current charge-discharge test (current density 100mA/g, 0.005~2.5V of voltage range) shows electric discharge Capacity is up to 2950mAh/g, and coulombic efficiency is 82% for the first time.

Claims (10)

1. a kind of silicon based anode material, which is characterized in that the silicon based anode material is by porous nano silicon particle and disperse in hole In polymer composition.
2. silicon based anode material according to claim 1, which is characterized in that the polymer is selected from polymerized thylene carbonate ethylene Ester.
3. silicon based anode material according to claim 1 or 2, which is characterized in that the size of the porous nano silicon particle For 10nm~500nm；By weight percentage, polymer is the 5%~25% of porous nano silicon particle.
4. a kind of preparation method of the described in any item silicon based anode materials of claim 1-3, which is characterized in that the preparation side Method includes the following steps
1) by after the raw material high-temperature heat treatment of silicon oxide-containing, pickling obtains pure silica；
2) pure silica obtained in step 1) is uniform through ball milling mixing with reducing metal and metal chloride；
3) mixture obtained by step 2) is placed in atmosphere protection stove, is passed through inert gas, carry out metallothermic reduction reaction, it is cooling To room temperature, metallothermic reduction product is obtained；
4) metallothermic reduction product obtained by step 3) is obtained into porous nano silicon after pickling, dry；
5) porous nano silicon obtained by step 4) is uniformly mixed with polymer monomer, initiator is added and carries out in-situ polymerization, obtains Silicon based anode material.
5. the preparation method according to claim 4, which is characterized in that in step 2), the reducing metal be magnesium metal, Metallic aluminium or metallic zinc；The metal chloride is one kind or several of sodium chloride, potassium chloride, magnesium chloride, zinc chloride or aluminium chloride Kind.
6. preparation method according to claim 5, which is characterized in that magnesium metal described in step 2) or metallic zinc and pure oxygen The molar ratio of SiClx is 2~2.1:1；The molar ratio of the metallic aluminium and pure silica is 4.0~4.3:3；The metal chlorination The weight ratio of object and silica is 5~10:1.
7. the preparation method according to claim 4, which is characterized in that the reaction of metallothermic reduction described in step 3) refers to temperature Degree reacts 2~20 hours under the conditions of being 500~900 DEG C.
8. the preparation method according to claim 4, which is characterized in that in-situ polymerization described in step 5) temperature be 50~ It is reacted 5~30 hours under the conditions of 90 DEG C.
9. the preparation method according to claim 4, which is characterized in that initiator described in step 5) is azo initiation Agent, the dosage of the initiator are as follows: 0.5~2 milligram of initiator is added in every milliliter of vinylene carbonate.
10. a kind of application of the silicon based anode material of any one of claim 4-9 the method preparation as battery material.
CN201811464722.7A 2018-12-03 2018-12-03 A kind of silicon based anode material and its preparation method and application Pending CN109585829A (en)

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CN114497485A (en) * 2022-01-07 2022-05-13 中南大学 Porous silicon-based composite material and preparation method and application thereof
CN117509646A (en) * 2023-11-13 2024-02-06 中国科学院广州地球化学研究所 Preparation method and device of silicon-based nano-micron material

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