CN106549149A - A kind of preparation method and application of Si-C composite material - Google Patents
A kind of preparation method and application of Si-C composite material Download PDFInfo
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- CN106549149A CN106549149A CN201610961548.1A CN201610961548A CN106549149A CN 106549149 A CN106549149 A CN 106549149A CN 201610961548 A CN201610961548 A CN 201610961548A CN 106549149 A CN106549149 A CN 106549149A
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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
- H01M4/366—Composites as layered products
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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
- 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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 preparation method and application of Si-C composite material, belongs to technical field of composite preparation.The preparation method, comprises the following steps：(1) silicon-base alloy is clayed into power, Jing pickling obtains porous silica material；(2) porous silica material is mixed with organic polymer carbon source and solvent, ball milling is obtained even paste mixture, after drying, heat treatment is obtained the Si-C composite material.The present invention is in carbon coating, using the high organic polymer carbon source of viscosity (such as Kynoar), be mixed and made into sticky colloid with a small amount of solvent, then coordinate ball milling make organic polymer carbon source effectively uniform adhesion in porous silicon surface, carbon coating it is in hgher efficiency；Organic solvent usage amount is few in addition, saves the energy that solvent is evaporated consumption, and then reduces production cost.Preparation process is simple, suitable large-scale production, the silicon-carbon accounting in obtained Si-C composite material rationally, with preferable bulk strain ability, lift the chemical property of lithium ion battery.
Description
Technical field
The present invention relates to technical field of composite preparation, and in particular to a kind of preparation method of Si-C composite material and should
With.
Background technology
Lithium ion battery is because with specific energy height, capacity is big, voltage is high, self discharge is little, good cycle, long service life
Become the ideal source of the portable electric appts such as notebook computer, mobile electronic device Deng outstanding advantages.In order to meet day
Become growth demand, to have high-energy-density, high power density, the new type lithium ion battery of long circulation life concurrently be current lithium for exploitation
One extremely important research direction of ion battery research field.
Silicon is a kind of new lithium ion battery negative material, and its storage lithium response voltage platform is relatively low, and theoretical capacity is high
(4200mAh/g), the graphite cathode (372mAh/g) of significantly larger than existing market, and silicon rich reserves in nature, be
The lithium ion battery negative material of the great development prospect of one class.But its own electrical conductivity is relatively low；In charge and discharge process, with lithium from
The embedded and abjection of son, silicon materials change in volume are larger, cause material efflorescence, come off, and ultimately result in and collector departs from, circulation
Less stable.
At present, by the nano-structured of silicon materials, porous and/or its further composite hybridization with material with carbon element, silicon
The instability problem that volume deformation causes is able to effectively solving to a certain extent, and electrode storage lithium characteristic has obtained carrying significantly
It is high.However, the preparation of these structured silicons or Si-C composite material is made in there is complex process, apparatus expensive and preparation process
The problems such as with highly toxic raw material.
The porous silicon preparation method reported in document has a lot, such as thermal reduction Si oxide method, acid corrosion silicon-base alloy
Method etc..Patent documentation such as CN102157731A discloses a kind of silicon-carbon composite cathode material of lithium ion battery and its preparation side
Method.The method first prepares porous silicon matrix using magnesiothermic reduction mesoporous silicon oxide, then carries out carbon coating, obtains silicon-carbon Compound Negative
Pole material.Mesoporous silicon oxide used by the method and magnesium powder high cost, are unfavorable for industrialized production.
Acid corrosion silicon-base alloy method has low cost, has more industrial prospect the advantages of process is simple is controllable.Such as CN
The patent documentation of 104617276 A discloses a kind of lithium rechargeable battery porous silicon/carbon compound cathode materials and its preparation side
Method, the preparation method, will be containing the SiO 2 powder of alkali (soil) metal chloride and aluminium oxidies first with pyrolytic carbon as reducing agent
One step of mixture of powders prepares silico-aluminum, then by which Jing after acid corrosion, vacuum drying, then organic polymer is mixed in graphite
In solution, solvent evaporated obtains final product porous silicon/carbon composite material after high-temperature roasting under last inert atmosphere.By silico-aluminum system
Silica alumina ratio and granular size are adjusted during standby, the hole size in final porous silicon/material with carbon element and pore size distribution can be controlled.This
Bright described porous silicon/material with carbon element has first that coulombic efficiency is high, has extended cycle life, the high feature of capacity.In the method, solvent steams
It is dry to need to consume mass energy, and the parcel of the organic polymer of such as glucose is not ideal enough.
Therefore a kind of process is simple, preparation method with low cost, being suitable for large-scale production are developed, and ensures the silicon for obtaining
Carbon composite has excellent electrochemical performance, is the problem that those skilled in the art need to solve.
The content of the invention
The invention provides a kind of preparation method of Si-C composite material, prepares porous silicon first with acid corrosion silicon-base alloy
Material, the organic polymer carbon source for recycling viscosity higher coordinate high-energy ball milling effectively to adhere to carbon source and wrap porous silicon
Material, obtains the Si-C composite material with excellent electrochemical performance after carbonization.
A kind of preparation method of Si-C composite material, comprises the following steps：
(1) silicon-base alloy is clayed into power, Jing pickling obtains porous silica material；
(2) porous silica material is mixed with organic polymer carbon source and solvent, ball milling is obtained even paste mixture, after drying
Heat treatment is obtained the Si-C composite material；
Described organic polymer carbon source be Kynoar, polypyrrole, tripolycyanamide, polyethylene glycol oxide, polyacrylonitrile,
One or more mixture in polystyrene, Polyethylene Glycol, polylactic acid, polycaprolactone, polymethyl methacrylate.
The present invention utilizes high-energy ball milling method efflorescence silicon-base alloy, and the grain diameter for reducing raw material not only contributes to follow-up acid
The carrying out of corrosion, and the specific surface area of porous silicon is increased, strengthen which and bear volume deformability.The rotating speed of the ball milling is
400～1200 revs/min, the time is 1～48h.
Except silicon in the silicon-base alloy, also including in ferrum, aluminum, copper, chromium, nickel, stannum, manganese, calcium, magnesium, cobalt, titanium and germanium
Plant or various.Above-mentioned metallic element can be compounded to form stable alloying or partially-alloyed compound, its good gold with silicon
Category ductility, contributes to improving the processing characteristics of silicon-base alloy.
Reasonable adjusting silicon and the accounting and granular size of other metals, can control hole size and the hole in porous silica material
Distribution.Preferably, the mass percentage content of silicon is 20～95% in the silicon-base alloy.
Preferably, except silicon in the silicon-base alloy, also including ferrum and/or aluminum.Corrosion of the acid to such silicon-base alloy
Effect is good, is conducive to the porous Si-C composite material that processability is good.More preferably, the silicon-base alloy is siliceous amount percentage
Than the Antaciron that content is 65～75%.
Preferably, the pickling is two road pickling, the acid that first pickling is adopted is in sulphuric acid, nitric acid or hydrochloric acid
Plant or various aqueous solutions, its molar concentration is 0.1～15mol/L；The acid that second pickling is adopted for hydrofluoric acid aqueous solution, its
Mass percent concentration is 1～20%.More preferably, first pickling adopts the sulfuric acid solution of 1mol/L, second pickling to adopt
With the hydrofluoric acid solution that mass fraction is 5%.
First pickling of the present invention is that, in order to remove the metallic element in silicon-base alloy, second pickling is to remove silica
Compound.Preferably, during pickling, in the immersion acid of silicon-base alloy powder, stir 10～20h, be collected by filtration product carrying out wash,
It is dried.Stirring is favorably improved the touch opportunity of acid and metal.
Preferably, the organic polymer carbon source is Kynoar, polypyrrole, polyacrylonitrile or polystyrene.This
Class polymer viscosity is high, is easily wrapped in porous silica material surface.
Preferably, the organic polymer carbon source of addition is calculated as 5～50% of siliceous amount in silicon-base alloy with the quality of carbon.
More preferably, the organic polymer carbon source of addition is calculated as 50% of siliceous amount in silicon-base alloy with the quality of carbon.It is described organic high
Molecule carbon source refers to the Mass Calculation of carbon that organic polymer carbon source is obtained Jing after carbonization as carbon matrix precursor using carbonaceous gauge.
In order that organic polymer carbon source effectively wraps porous silica material, can be properly added solvent makes organic polymer carbon
Dissolve in source.The solvent is toluene, chlorobenzene, dimethylbenzene, dichloromethane, hexamethylene, methanol, ethanol, ethylene glycol, isopropanol, second
Ether, expoxy propane, methyl acetate, pyridine, tetrahydrofuran, carbon tetrachloride, acetonitrile, dimethylformamide, N-Methyl pyrrolidone
In any one or two or more mixing.
Preferably, the solvent is N-Methyl pyrrolidone or pyridine, the organic polymer carbon source is mixed with solvent
It is 1 to close mass ratio:1～5:1.The energy of consumption is evaporated to save solvent, the addition of solvent is with organic polymer carbon source system
Into sticky glue, the mixing of later use high-energy ball milling can by gluey carbon source uniform adhesion on porous silica material surface,
More preferably, organic polymer carbon source is 5 with the mixing quality ratio of solvent:1.
The condition of the ball milling：Ball material mass ratio is 4～5:1, rotating speed is 500～600 revs/min, and the time is 8～10h.
Preferably, in step (2), the condition of the heat treatment：Under non-oxygen atmosphere, 400～1200 DEG C of insulations 1～12
Hour.More preferably, the heat treatment condition：In nitrogen environment, 800 DEG C are heated to the heating rate of 5 DEG C/min, be incubated
5h。
After heat treatment terminates, naturally cool to room temperature, collect product and deionized water and absolute ethanol washing for several times, then
The Si-C composite material that the present invention is obtained is dried in vacuum drying box.Preferably, vacuum drying temperature is 60～120
DEG C, the time is 2～12h.
Present invention also offers by obtained in above-mentioned preparation method Si-C composite material, wherein the content of silicon be 5～50%,
Loose structure, the effectively volumetric expansion of buffering silicon are presented, the carbon of silicon face cladding enhances the conductive and electrochemistry of composite
Performance.
Present invention also offers a kind of lithium ion battery negative material, is made up of active substance, conductive agent and binding agent, institute
It is the Si-C composite material by obtained in above-mentioned preparation method to state active substance.The conductive agent for adopting and binding agent are for existing conventional material
Material, such as conductive carbon black (super-p), Kynoar (PVDF).
The beneficial effect that the present invention possesses：
(1) present invention is in carbon coating, using the high organic polymer carbon source (such as Kynoar) of viscosity, molten with a small amount of
Agent is mixed and made into sticky colloid, then coordinate ball milling make organic polymer carbon source effectively uniform adhesion in porous silicon surface, carbon
What is coated is in hgher efficiency；Organic solvent usage amount is few in addition, saves the energy that solvent is evaporated consumption, and then reduces production cost.
(2) preparation process is simple of the present invention, large-scale production with low cost, suitable, and obtained Si-C composite material
In silicon-carbon accounting rationally, with preferable bulk strain ability, lift the chemical property of lithium ion battery.
Description of the drawings
Fig. 1 is the Raman spectrogram of Si-C composite material prepared by embodiment 1.
Fig. 2 is the performance test energy of lithium ion battery prepared by embodiment 1.
Fig. 3 is the performance test figure of lithium ion battery prepared by embodiment 2.
Fig. 4 is the performance test figure of lithium ion battery prepared by comparative example 1.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
1st, the preparation of Si-C composite material
It is little particle the Antaciron that 1g silicone contents are 65% to be crushed using planetary ball mill, wherein, ball material quality
Than being about 4:1, rotating speed is 500 revs/min, and Ball-milling Time obtains Antaciron powder after 6 hours.
The Antaciron material for obtaining is placed in beaker, the sulphuric acid that excessive molar concentration is 1mol/L is added, normal
Temperature is lower to remove ferrous metal element for 24 hours using magnetic stirrer, and product is cleaned 3 times using deionized water；Then will
Product add it is excessive containing mass fraction be 5% hydrofluoric acid solution in remove Si oxide, magnetic agitation 12 hours under room temperature,
Product is respectively washed 3 times using deionized water and Fluohydric acid. and obtains porous silica material.
Kynoar containing 5g and 1gN- methyl pyrrolidones are added to the porous silicon composite material for obtaining, profit under room temperature
Silicon/organic polymer alloy composite materials are obtained for 6 hours with 500 revs/min of rotating speed ball milling with ball mill, by silicon/organic high score
Sub- alloy composite materials are all evaporated, and are placed in tube furnace, in nitrogen environment are heated to 800 with the heating rate of 5 DEG C/min
DEG C, 5 hours are incubated, room temperature is naturally cooled to；Deionized water and ethanol are washed 3 times respectively again, in vacuum drying oven at 100 DEG C
Drying obtains Si-C composite material in 5 hours.
Obtained Si-C composite material carries out Raman spectrum analyses, as a result as shown in Figure 1.
2nd, the preparation of Si-C composite material negative pole
Sample will be prepared by Si-C composite material (active material)：Conductive agent (conductive carbon black, super-p)：
Binding agent (Kynoar, PVDF)=8:1:1 mass ratio mixing, adds a certain amount of N-Methyl pyrrolidone (NMP) molten
Agent, using magnetic agitation mix homogeneously.Slurry is coated uniformly on Copper Foil using coating machine, in vacuum drying oven 100 DEG C it is true
It is empty to be dried 10 hours, after through tabletting, section, be dried, weigh etc. and to obtain pole piece, battery to be assembled.
3rd, the preparation of lithium ion battery and test
Dry pole piece is put into into assembled battery in the glove box containing high-purity argon gas, in the button cell of assembling, just extremely
Si-C composite material, negative pole are lithium piece, and barrier film is polypropylene screen, and electrolyte is the lithium hexafluoro phosphate containing lithium salts for 1mol/L
(LiPF6), solvent is that volume ratio is 1:1:1 ethylene carbonate (EC)：Dimethyl carbonate (DMC)：Ethyl methyl carbonate (EMC).
Charge-discharge test is carried out to lithium ion battery using the constant current of blue electrical measurement test system, test density electric current is 0.2c.As a result such as Fig. 2 institutes
Show.
Embodiment 2
1st, the preparation of Si-C composite material
It is little particle the Antaciron that 5g silicone contents are 75% to be crushed using planetary ball mill, wherein, ball material quality
Than being about 4:1, rotating speed is 550 revs/min, and Ball-milling Time obtains Antaciron powder after 8 hours.
The Antaciron material for obtaining is placed in beaker, the sulphuric acid that excessive molar concentration is 1mol/L is added, normal
Temperature is lower to remove ferrous metal element for 24 hours using magnetic stirrer, and product is cleaned 3 times using deionized water；Then will
Product add it is excessive containing mass fraction be 5% hydrofluoric acid solution in remove Si oxide, magnetic agitation 12 hours under room temperature,
Product is respectively washed 3 times using deionized water and Fluohydric acid. and obtains porous silica material.
Polyacrylonitrile containing 7g and 1.5g pyridines are added to the porous silicon composite material for obtaining, under room temperature using ball mill with
550 revs/min of rotating speed ball milling obtains silicon/organic polymer alloy composite materials for 8 hours, and silicon/organic polymer alloy is combined
Material is all evaporated, and is placed in tube furnace, in nitrogen environment is heated to 800 DEG C with the heating rate of 5 DEG C/min, and insulation 5 is little
When, naturally cool to room temperature；Deionized water and ethanol are washed 3 times respectively again, are dried 5 hours in vacuum drying oven at 100 DEG C
Obtain Si-C composite material.
2nd, the preparation of Si-C composite material negative pole
Sample will be prepared by Si-C composite material (active material)：Conductive agent (conductive carbon black, super-p)：
Binding agent (Kynoar, PVDF)=8:1:1 mass ratio mixing, adds a certain amount of N-Methyl pyrrolidone (NMP) molten
Agent, using magnetic agitation mix homogeneously.Slurry is coated uniformly on Copper Foil using coating machine, in vacuum drying oven 100 DEG C it is true
It is empty to be dried 10 hours, after through tabletting, section, be dried, weigh etc. and to obtain pole piece, battery to be assembled.
3rd, the preparation of lithium ion battery and test
Dry pole piece is put into into assembled battery in the glove box containing high-purity argon gas, in the button cell of assembling, just extremely
Si-C composite material, negative pole are lithium piece, and barrier film is polypropylene screen, and electrolyte is the lithium hexafluoro phosphate containing lithium salts for 1mol/L
(LiPF6), solvent is that volume ratio is 1:1:1 ethylene carbonate (EC)：Dimethyl carbonate (DMC)：Ethyl methyl carbonate (EMC).
Charge-discharge test is carried out to lithium ion battery using the constant current of blue electrical measurement test system, test density electric current is 0.5c.As a result such as Fig. 3 institutes
Show that lithium ion battery manufactured in the present embodiment is recycled to 600 circles, capability retention reaches 80%.
Comparative example 1
5g Kynoar, solvent is replaced to adopt deionized water using 30g glucoses when Si-C composite material is prepared, its
His raw material, consumption and preparation method prepares lithium ion battery and method of testing with reference to embodiment 1 with embodiment 1.Test result
As shown in figure 4, find with the results contrast of embodiment 1, should as the Si-C composite material that carbon wraps up raw material preparation using glucose
Use in lithium battery, its specific capacity easily decays as lithium battery obtained in carbon source, and capacity less than inclined tetrafluoroethene is gathered.
The explanation of book according to the above description, those skilled in the art in the invention can also be carried out to above-mentioned embodiment
Appropriate modifications and changes, therefore, all any modification, supplement or similar fashions made in the spirit of the present invention are replaced
In generation etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of Si-C composite material, it is characterised in that comprise the following steps：
(1) silicon-base alloy is clayed into power, Jing pickling obtains porous silica material；
(2) porous silica material is mixed with organic polymer carbon source and solvent, ball milling is obtained even paste mixture, after drying at heat
Reason is obtained the Si-C composite material；
Described organic polymer carbon source be Kynoar, polypyrrole, tripolycyanamide, polyethylene glycol oxide, polyacrylonitrile, poly- third
One or more mixture in ethylene, Polyethylene Glycol, polylactic acid, polycaprolactone, polymethyl methacrylate.
2. preparation method as claimed in claim 1, it is characterised in that the mass percentage content of silicon is in the silicon-base alloy
20～95%.
3. preparation method as claimed in claim 2, it is characterised in that except silicon in the silicon-base alloy, also including ferrum and/or
Aluminum.
4. preparation method as claimed in claim 1, it is characterised in that the pickling is two road pickling, first pickling is adopted
Acid be one or more of aqueous solution in sulphuric acid, nitric acid or hydrochloric acid, its molar concentration is 0.1～15mol/L；Second acid
The acid for adopting is washed for hydrofluoric acid aqueous solution, its mass percent concentration is 1～20%.
5. preparation method as claimed in claim 4, it is characterised in that during pickling, in the immersion acid of silicon-base alloy powder, stirring 10
～20h, is collected by filtration product and carries out washing, is dried.
6. preparation method as claimed in claim 1, it is characterised in that in step (2), the organic polymer carbon source are poly- inclined
Fluorothene, polypyrrole, polyacrylonitrile or polystyrene.
7. preparation method as claimed in claim 1, it is characterised in that in step (2), the organic polymer carbon source of addition is with carbon
Quality be calculated as 5～50% of siliceous amount in silicon-base alloy.
8. preparation method as claimed in claim 1, it is characterised in that in step (2), the solvent are N-Methyl pyrrolidone
Or pyridine, the organic polymer carbon source is 1 with the mixing quality ratio of solvent:1～5:1.
9. preparation method as claimed in claim 1, it is characterised in that in step (2), the condition of the heat treatment：In non-oxygen
Under atmosphere, 400～1200 DEG C are incubated 1～12 hour.
10. a kind of lithium ion battery negative material, is made up of active substance, conductive agent and binding agent, it is characterised in that the work
Property material is Si-C composite material obtained in the preparation method by described in any one of claim 1-9.
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| CN106935834A (en) * | 2017-04-21 | 2017-07-07 | 山东大学 | A kind of porous silicon negative material of compound carbon coating and preparation method thereof |
| CN107507972A (en) * | 2017-08-29 | 2017-12-22 | 北方奥钛纳米技术有限公司 | Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material |
| CN108232165A (en) * | 2018-01-16 | 2018-06-29 | 苏州大学 | A kind of preparation method of carbon-silicon composite material |
| CN109473648A (en) * | 2018-11-02 | 2019-03-15 | 中国有色桂林矿产地质研究院有限公司 | A kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof |
| CN109755507A (en) * | 2018-12-18 | 2019-05-14 | 湘潭大学 | A kind of preparation method of lithium ion battery silicon/carbon composite aerogel negative electrode material |
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| CN116161665A (en) * | 2023-02-28 | 2023-05-26 | 赣州市瑞富特科技有限公司 | Preparation method of porous silicon/alumina/amorphous carbon composite material and application of porous silicon/alumina/amorphous carbon composite material in lithium ion battery |
| CN117117159A (en) * | 2023-10-24 | 2023-11-24 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
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| CN110335993A (en) * | 2019-05-17 | 2019-10-15 | 大连理工大学 | A kind of porous silicon/oxidative silicon/carbon composite of the ball shaped nano of lithium ion battery and preparation method thereof |
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| CN110289402A (en) * | 2019-06-10 | 2019-09-27 | 中国科学院合肥物质科学研究院 | It is crosslinked the electrode material and preparation method thereof of the mesoporous silicon particle of carbon coating |
| CN110289402B (en) * | 2019-06-10 | 2022-09-16 | 中国科学院合肥物质科学研究院 | Electrode material of crosslinked carbon-coated mesoporous silicon particles and preparation method thereof |
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| CN110854374A (en) * | 2019-11-26 | 2020-02-28 | 石家庄昭文新能源科技有限公司 | Porous carbon coated ferrosilicon alloy material and preparation method and application thereof |
| CN111653739A (en) * | 2020-04-28 | 2020-09-11 | 万向一二三股份公司 | Method for preparing high-cycle-performance SiO negative electrode material of lithium battery |
| CN112614973A (en) * | 2020-12-07 | 2021-04-06 | 惠州市豪鹏科技有限公司 | Silicon-carbon negative electrode material and preparation method thereof, negative plate and lithium ion battery |
| CN112599778A (en) * | 2020-12-15 | 2021-04-02 | 广东凯金新能源科技股份有限公司 | Silicon-carbon-based negative electrode material and preparation method thereof |
| CN114763260A (en) * | 2021-01-14 | 2022-07-19 | 中国科学院广州能源研究所 | High-pore-volume fluorine-doped hollow carbon sphere and preparation method and application thereof |
| CN114763260B (en) * | 2021-01-14 | 2023-09-05 | 中国科学院广州能源研究所 | Fluorine-doped hollow carbon sphere with high pore volume and preparation method and application thereof |
| CN116161665A (en) * | 2023-02-28 | 2023-05-26 | 赣州市瑞富特科技有限公司 | Preparation method of porous silicon/alumina/amorphous carbon composite material and application of porous silicon/alumina/amorphous carbon composite material in lithium ion battery |
| CN117117159A (en) * | 2023-10-24 | 2023-11-24 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
| CN117117159B (en) * | 2023-10-24 | 2023-12-26 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
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Application publication date: 20170329 |