CN110289402A - It is crosslinked the electrode material and preparation method thereof of the mesoporous silicon particle of carbon coating - Google Patents
It is crosslinked the electrode material and preparation method thereof of the mesoporous silicon particle of carbon coating Download PDFInfo
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- 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
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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- 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 electrode materials and preparation method thereof for being crosslinked the mesoporous silicon particle of carbon coating.Material is 20-100m by specific surface area2The surface cladding of/g is crosslinked with the mesoporous silicon particle composition of carbon, wherein the partial size of mesoporous silicon particle is 0.2-5 μm, and mesoporous aperture thereon is 2-50nm, and the weight ratio between mesoporous silicon particle and carbon is 100:1-30；Method is that breaked alusil alloy is first placed in progress liquid phase ball milling in ball mill, after obtained alusil alloy powder and acid solution are mixed again, it is dry after obtained mesoporous silicon particle, cationic surfactant and organic carbon source solution are mixed, obtain intermediate product, later, intermediate product is placed in reducing atmosphere and is calcined, purpose product is made.It has higher reversible specific capacity, charge and discharge cycles stability and high rate performance and high storage lithium cycle performance, is extremely easy to widely be commercialized the negative electrode material as lithium ion battery.
Description
Technical field
The present invention relates to a kind of silicon-carbon electrode material and preparation method, especially a kind of crosslinking mesoporous silicon particle of carbon coating
Electrode material and preparation method thereof.
Background technique
Environmental problem brought by fossil energy is used not with the continuous consumption of traditional fossil energy, and without limit
Disconnected aggravation, the sustainable new energy of development health have gradually become the common recognition of the mankind.In recent years, the various new energy such as sun
The renewable and clean energy resources such as energy, wind energy, tide energy, geothermal energy have obtained quick development, use specific gravity in daily life
Also it is stepping up.However, since clean energy resource is there is unstability and discontinuity is supplied, to large-scale
Popularization and use bring great limitation.Thus, the unstable energy of this kind of cleaning is first stored and has rationally been output into head again
The plan of the reply of choosing, thus researches and develops large capacity, can the electrochmical power source systems of charge and discharge become hot spot concerned by people.
In many secondary cells, lithium ion battery is because having long-life, higher energy density, light-weight, volume
It is small, be concerned using the advantages that safe, environmentally protective, be widely used.Currently, as negative electrode of lithium ion battery
The graphite of mainstay material, because of its lower capacity (theoretical specific capacity 372mAh/g, practical reversible specific capacity are 330mAh/g)
It is difficult to meet the requirement of energy storage device and power big battery high-energy density；For this purpose, people are to obtain to have height ratio capacity and height
The negative electrode material of power density, is made that unremitting effort, if 105226285 B of Chinese invention patent CN is in October, 2017
A kind of porous Si-C composite material and preparation method thereof of bulletin on the 17th.The porous Si-C composite material referred in the patent of invention
It is formed by being covered with carbon on porous silicon particle, specific surface area 10-500cm2/ g, the partial size of porous silicon particle are 5-
500nm；Preparation method is active metal and the silica first successively removed in silicon alloy, then by the porous silicon and polymer of acquisition
It mixes and is calcined after carrying out ball milling, obtain product.Though this product has higher reversible specific capacity and charge and discharge cycles to stablize
Property, but all there is shortcomings with preparation method, firstly, the specific surface area of product is too low, not only constrain storage lithium circulation
Performance also limits electric conductivity；Secondly, the connection between porous silicon particle in product and the carbon being covered with thereon is not crosslinking
Connection, it is also unfavorable to the stability of product structure and persistence other than influencing the rate of charge and discharge；Again, preparation method
The product with higher reversible specific capacity and charge and discharge cycles stability cannot be obtained.
Summary of the invention
The technical problem to be solved in the present invention place in order to overcome the shortcomings in the prior art, provide it is a kind of have it is higher can
The electrode material of the mesoporous silicon particle of crosslinking carbon coating of inverse specific capacity and charge and discharge cycles stability and high rate performance.
The invention solves another technical problem be that a kind of electrode of above-mentioned mesoporous silicon particle of crosslinking carbon coating is provided
The preparation method of material.
To solve technical problem of the invention, used technical solution is to be crosslinked the electrode of the mesoporous silicon particle of carbon coating
Material is formed by being covered with carbon on porous silicon particle, especially:
The porous silicon particle is mesoporous silicon particle, and the partial size of the mesoporous silicon particle is 0.2-5 μm, thereon mesoporous
Aperture is 2-50nm；
Weight ratio between the mesoporous silicon particle and carbon is 100:1-30, and the weight ratio is the mesoporous of 100:1-30
The surface cladding of silicon particle is crosslinked with carbon；
The specific surface area for the mesoporous silicon particle that the surface cladding is crosslinked with carbon is 20-100m2/g。
The further improvement of electrode material as the crosslinking mesoporous silicon particle of carbon coating:
Preferably, the weight ratio between mesoporous silicon particle and carbon is 100:4-20.
To solve another technical problem of the invention, another used technical solution is above-mentioned crosslinking carbon coating
The preparation method of the electrode material of mesoporous silicon particle includes ball-milling method, and especially steps are as follows for completion:
Step 1, first aluminium, the alusil alloy that silicon weight percent is 60-10wt%:40-90wt% are crushed, then are set
In ball mill, liquid phase ball milling is carried out according to the ratio that ratio of grinding media to material is 40-10:1, liquid-to-solid ratio is 1-10mL/g, obtaining partial size is
0.2-5 μm of alusil alloy powder；
Step 2, the ratio for being first 1:1-2 according to the weight ratio of alusil alloy powder, the acid solution of 1-5mol/L, by the two
It is placed at 35-45 DEG C and at least 4h is mixed, obtain mesoporous silicon particle, according still further to mesoporous silicon particle, cationic surfactant
The ratio that weight ratio with organic carbon source solution is 1:0.01-0.001:2-5, will be dry after three's mixing at least 2h, obtains
To intermediate product；
Step 3, intermediate product is placed in reducing atmosphere, at least 2h is calcined at 500-900 DEG C, crosslinking carbon packet is made
Cover the electrode material of mesoporous silicon particle.
The further improvement of the preparation method of electrode material as the crosslinking mesoporous silicon particle of carbon coating:
Preferably, the material of ball grinder and abrading-ball is one or more of agate, zirconium oxide, stainless steel, corundum
Mixture.
Preferably, the liquid phase medium of ball milling be one of ethyl alcohol, methanol, polyglycols, N-Methyl pyrrolidone, kerosene or
Two or more mixtures.
Preferably, acid solution is hydrochloric acid solution, sulfuric acid solution, nitric acid solution, glacial acetic acid solution, phosphoric acid solution, tri-chlorination
The mixture of one or more of ferrous solution.
Preferably, cationic surfactant is polyetherimide, polyetheramine, dopamine, laurylamine hydrochloride, 12
Amine, octadecylamine, Quaternary Polyethyleneimine, tertiary amine polyethyleneimine, dodecyl trimethyl ammonium chloride, dodecyl front three
Base ammonium bromide, hexadecyltrimethylammonium chloride, polyethyleneimine, dodecyl dimethyl benzyl ammonium chloride, Cetylpyridinium chloride
The mixture of one or more of base dimethyl benzyl ammonium.
Preferably, organic carbon source solution is sucrose solution, glucose solution, chitosan solution, starch solution, polyethylene pyrrole
One or both of pyrrolidone solution, polyacrylonitrile solution, citric acid solution, phenol resin solution, polyglycol solution with
On mixture.
Preferably, dry temperature is 100-200 DEG C, time 2-4min.
Preferably, reducing atmosphere is hydrogen atmosphere, nitrogen atmosphere, argon atmosphere, helium atmosphere, one in neon atmosphere
Kind or two or more mixed atmospheres.
Beneficial effect compared with the existing technology is:
First, using scanning electron microscope, transmission electron microscope and specific surface and porosity analyser respectively to purpose product obtained
It is characterized, by its result and combines preparation method it is found that the surface cladding that purpose product is mesoporous silicon particle is crosslinked with carbon member
Element；Wherein, the partial size of mesoporous silicon particle is 0.2-5 μm, and mesoporous aperture thereon is 2-50nm, mesoporous silicon particle and carbon
Between weight ratio be 100:1-30, surface cladding be crosslinked with carbon mesoporous silicon particle specific surface area be 20-100m2/g。
This purpose product being assembled by mesoporous silicon particle and the carbon being crosslinked with its surface cladding, both at normal temperature due to silicon
The Li of 3572mAh/g can be up to lithium alloyage, generative theory specific capacity15Si4Phase, and because silicon particle is to compare table with high
The mesoporous silicon particle of area, due also to the electric conductivity of carbon is splendid, and close with the chemical property of silicon, more because of mesoporous silicon particle
It is surface cladding crosslinking connection between carbon, and makes using purpose product as when negative electrode of lithium ion battery, in the mistake of charge and discharge
Cheng Zhong is not only easy to lithium ion and shuttles penetrate the carbon coating layer on surface repeatedly, due also to Jie numerous in mesoporous silicon particle
Hole gap has effectively buffered silicon core while increasing and storing up lithium performance and has absorbed or releasing the enormousness occurred after lithium ion
Change the destruction generated to silicon core, greatly improves performance and charge and discharge of the purpose product as negative electrode of lithium ion battery when
Electric cycle life.
Second, being assembled into 2032 using raw material same as the prior art using purpose product obtained as negative electrode material
Button cell, and in the occasion China electrochemical workstation and model CT-4008 that use model 660E respectively under the same conditions
New prestige battery test system tested, as a result: first discharge specific capacity 3266.41mAh/g, charge specific capacity are
2566.72mAh/g coulombic efficiency may be up to 79.6% for the first time；Secondary specific discharge capacity is 2644.54mAh/g, charge ratio
Capacity is 2470.41mAh/g, and coulombic efficiency may be up to 93.4%.830mA/g current density is used after 80mA/g charge and discharge twice
Charge/discharge test is carried out, test result shows preferable cyclical stability.Multiplying power test is carried out to 2032 button cells,
The current density discharge capacity of 330mA/g is about 2250mAh/g, and the discharge capacity under the current density of 3300mA/g is about
750mAh/g。
Third, preparation method is simple, scientific, efficient.It has not only been made and has been followed with higher reversible specific capacity and charge and discharge
The purpose product of ring stability and high rate performance --- the electrode material of the crosslinking mesoporous silicon particle of carbon coating also makes it have
High storage lithium cycle performance, more there is the characteristics of low manufacture cost；And then purpose product is made to be extremely easy to widely be commercialized use
Make the negative electrode material of lithium ion battery.
Detailed description of the invention
Fig. 1 is to use purpose product made from preparation method scanning electron microscope (SEM) and specific surface and porosity point respectively
One of the result that analyzer is characterized.Wherein, a figure in Fig. 1 is the SEM image of mesoporous silicon particle；B figure is mesoporous silicon particle
Graph of pore diameter distribution.
Fig. 2 be use purpose product obtained scanning electron microscope and transmission electron microscope (TEM) to be characterized respectively result it
One.Wherein, a figure in Fig. 2 is the SEM image of purpose product；B figure is the TEM image of purpose product.
Fig. 3 is one of the result characterized to purpose product obtained using specific surface and porosity analyser.This knot
Fruit --- nitrogen adsorption-desorption isothermal curve chart bright purpose product specific surface area is 20-100m2/g。
Fig. 4 is the knot tested using the new prestige battery test system of model CT-4008 purpose product obtained
One of fruit.It follows that after purpose product charge and discharge cycles 200 times, still there is high charging and discharging capacity and preferably
Coulombic efficiency.
Specific embodiment
Preferred embodiment of the invention is described in further detail with reference to the accompanying drawing.
It buys from market or is voluntarily made first:
Agate, zirconium oxide, stainless steel and the corundum of material as ball grinder and abrading-ball；
Ethyl alcohol, methanol, polyglycols, N-Methyl pyrrolidone and the kerosene of liquid phase medium as ball milling；
As the hydrochloric acid solution of acid solution, sulfuric acid solution, nitric acid solution, glacial acetic acid solution, phosphoric acid solution and ferric trichloride
Solution；
As the polyetherimide of cationic surfactant, polyetheramine, dopamine, laurylamine hydrochloride, lauryl amine,
Octadecylamine, Quaternary Polyethyleneimine, tertiary amine polyethyleneimine, dodecyl trimethyl ammonium chloride, trimethyl
Ammonium bromide, hexadecyltrimethylammonium chloride, polyethyleneimine, dodecyl dimethyl benzyl ammonium chloride and hexadecyl
Dimethyl benzyl ammonium；
As the sucrose solution of organic carbon source solution, glucose solution, chitosan solution, starch solution, polyvinyl pyrrole
Alkanone solution, polyacrylonitrile solution, citric acid solution, phenol resin solution and polyglycol solution；
As the hydrogen of reducing atmosphere, nitrogen, argon gas, helium and neon.
Then:
Embodiment 1
The specific steps of preparation are as follows:
Step 1, first aluminium, the alusil alloy that silicon weight percent is 60wt%:40wt% are crushed.Ball milling is placed it in again
In machine, liquid phase ball milling is carried out according to the ratio that ratio of grinding media to material is 40:1, liquid-to-solid ratio is 10mL/g；Wherein, the material of ball grinder and abrading-ball
Matter is zirconium oxide, and the liquid phase medium of ball milling is ethyl alcohol, obtains the alusil alloy powder that partial size is 0.2 μm.
Step 2, the ratio for being first 1:2 according to the weight ratio of alusil alloy powder, the acid solution of 1mol/L, the two is placed in
12h is mixed at 35 DEG C；Wherein, acid solution is hydrochloric acid solution, obtains mesoporous silicon particle.According still further to mesoporous silicon particle, sun from
The weight ratio of sub- surfactant and organic carbon source solution is the ratio of 1:0.01:5, will be dry after three's mixing 2h；Its
In, cationic surfactant is polyetherimide, and organic carbon source solution is sucrose solution, and dry temperature is 100 DEG C, the time
For 4min, intermediate product is obtained.
Step 3, intermediate product is placed in reducing atmosphere, calcines 4h at 500 DEG C；Wherein, reducing atmosphere is nitrogen
Gas atmosphere.It is made and is similar to shown in Fig. 2, and be crosslinked the electricity of the mesoporous silicon particle of carbon coating as shown in the curve in Fig. 3 and Fig. 4
Pole material.
Embodiment 2
The specific steps of preparation are as follows:
Step 1, first aluminium, the alusil alloy that silicon weight percent is 48wt%:52wt% are crushed.Ball milling is placed it in again
In machine, liquid phase ball milling is carried out according to the ratio that ratio of grinding media to material is 33:1, liquid-to-solid ratio is 8.8mL/g；Wherein, the material of ball grinder and abrading-ball
Matter is zirconium oxide, and the liquid phase medium of ball milling is ethyl alcohol, obtains the alusil alloy powder that partial size is 0.8 μm.
Step 2, the ratio for being first 1:1.75 according to the weight ratio of alusil alloy powder, the acid solution of 2mol/L, by the two
It is placed at 38 DEG C and 10h is mixed；Wherein, acid solution is hydrochloric acid solution, obtains mesoporous silicon particle.According still further to mesoporous silicon particle,
The weight ratio of cationic surfactant and organic carbon source solution is the ratio of 1:0.008:4, is done after 3h is mixed in three
It is dry；Wherein, cationic surfactant is polyetherimide, and organic carbon source solution is sucrose solution, and dry temperature is 125
DEG C, time 3.5min obtains intermediate product.
Step 3, intermediate product is placed in reducing atmosphere, calcines 3.5h at 600 DEG C；Wherein, reducing atmosphere is
Nitrogen atmosphere.It is made and is similar to shown in Fig. 2, and the crosslinking mesoporous silicon particle of carbon coating as shown in the curve in Fig. 3 and Fig. 4
Electrode material.
Embodiment 3
The specific steps of preparation are as follows:
Step 1, first aluminium, the alusil alloy that silicon weight percent is 35wt%:65wt% are crushed.Ball milling is placed it in again
In machine, liquid phase ball milling is carried out according to the ratio that ratio of grinding media to material is 25:1, liquid-to-solid ratio is 6.5mL/g；Wherein, the material of ball grinder and abrading-ball
Matter is zirconium oxide, and the liquid phase medium of ball milling is ethyl alcohol, obtains the alusil alloy powder that partial size is 1 μm.
Step 2, the ratio for being first 1:1.5 according to the weight ratio of alusil alloy powder, the acid solution of 3mol/L, the two is set
8h is mixed at 40 DEG C；Wherein, acid solution is hydrochloric acid solution, obtains mesoporous silicon particle.According still further to mesoporous silicon particle, sun from
The weight ratio of sub- surfactant and organic carbon source solution is the ratio of 1:0.005:3, will be dry after three's mixing 4h；Its
In, cationic surfactant is polyetherimide, and organic carbon source solution is sucrose solution, and dry temperature is 150 DEG C, the time
For 3min, intermediate product is obtained.
Step 3, intermediate product is placed in reducing atmosphere, calcines 3h at 700 DEG C；Wherein, reducing atmosphere is nitrogen
Gas atmosphere.Be made as shown in Fig. 2, and such as the curve in Fig. 3 and Fig. 4 shown in crosslinking the mesoporous silicon particle of carbon coating electrode material
Material.
Embodiment 4
The specific steps of preparation are as follows:
Step 1, first aluminium, the alusil alloy that silicon weight percent is 23wt%:77wt% are crushed.Ball milling is placed it in again
In machine, liquid phase ball milling is carried out according to the ratio that ratio of grinding media to material is 18:1, liquid-to-solid ratio is 3.3mL/g；Wherein, the material of ball grinder and abrading-ball
Matter is zirconium oxide, and the liquid phase medium of ball milling is ethyl alcohol, obtains the alusil alloy powder that partial size is 3 μm.
Step 2, the ratio for being first 1:1.35 according to the weight ratio of alusil alloy powder, the acid solution of 4mol/L, by the two
It is placed at 43 DEG C and 6h is mixed；Wherein, acid solution is hydrochloric acid solution, obtains mesoporous silicon particle.According still further to mesoporous silicon particle, sun
The weight ratio of ionic surface active agent and organic carbon source solution is the ratio of 1:0.003:2, will be dry after three's mixing 5h；
Wherein, cationic surfactant is polyetherimide, and organic carbon source solution is sucrose solution, and dry temperature is 175 DEG C, when
Between be 2.5min, obtain intermediate product.
Step 3, intermediate product is placed in reducing atmosphere, calcines 2.5h at 800 DEG C；Wherein, reducing atmosphere is
Nitrogen atmosphere.It is made and is similar to shown in Fig. 2, and the crosslinking mesoporous silicon particle of carbon coating as shown in the curve in Fig. 3 and Fig. 4
Electrode material.
Embodiment 5
The specific steps of preparation are as follows:
Step 1, first aluminium, the alusil alloy that silicon weight percent is 10wt%:90wt% are crushed.Ball milling is placed it in again
In machine, liquid phase ball milling is carried out according to the ratio that ratio of grinding media to material is 10:1, liquid-to-solid ratio is 1mL/g；Wherein, the material of ball grinder and abrading-ball
It is zirconium oxide, the liquid phase medium of ball milling is ethyl alcohol, obtains the alusil alloy powder that partial size is 5 μm.
Step 2, the ratio for being first 1:1 according to the weight ratio of alusil alloy powder, the acid solution of 5mol/L, the two is placed in
4h is mixed at 45 DEG C；Wherein, acid solution is hydrochloric acid solution, obtains mesoporous silicon particle.According still further to mesoporous silicon particle, cation
The weight ratio of surfactant and organic carbon source solution is the ratio of 1:0.001:2, will be dry after three's mixing 6h；Its
In, cationic surfactant is polyetherimide, and organic carbon source solution is sucrose solution, and dry temperature is 200 DEG C, the time
For 2min, intermediate product is obtained.
Step 3, intermediate product is placed in reducing atmosphere, calcines 2h at 900 DEG C；Wherein, reducing atmosphere is nitrogen
Gas atmosphere.It is made and is similar to shown in Fig. 2, and be crosslinked the electricity of the mesoporous silicon particle of carbon coating as shown in the curve in Fig. 3 and Fig. 4
Pole material.
Select one of the agate of material as ball grinder and abrading-ball, zirconium oxide, stainless steel, corundum or two respectively again
Kind or more mixture, the ethyl alcohol of the liquid phase medium as ball milling, methanol, polyglycols, N-Methyl pyrrolidone, one in kerosene
Kind or two or more mixtures, it is molten as the hydrochloric acid solution of acid solution, sulfuric acid solution, nitric acid solution, glacial acetic acid solution, phosphoric acid
The mixture of one or more of liquid, liquor ferri trichloridi, the polyetherimide, poly- as cationic surfactant
Ether amines, dopamine, laurylamine hydrochloride, lauryl amine, octadecylamine, Quaternary Polyethyleneimine, tertiary amine polyethyleneimine, ten
Dialkyl group trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, hexadecyltrimethylammonium chloride, polyethyleneimine, chlorination
The mixture of one or more of dodecyl dimethyl hexadecyldimethyl benzyl ammonium, cetalkonium chloride, as
The sucrose solution of organic carbon source solution, glucose solution, chitosan solution, starch solution, polyvinylpyrrolidonesolution solution, poly- third
The mixture of one or more of alkene nitrile solution, citric acid solution, phenol resin solution, polyglycol solution, as
One or more of the hydrogen atmosphere of reducing atmosphere, nitrogen atmosphere, argon atmosphere, helium atmosphere, neon atmosphere
Mixed atmosphere repeats above-described embodiment 1-5, has equally been made as or has been similar to shown in Fig. 2, and such as the curve in Fig. 3 and Fig. 4
Shown in be crosslinked the mesoporous silicon particle of carbon coating electrode material.
Obviously, those skilled in the art can electrode material to the mesoporous silicon particle of crosslinking carbon coating of the invention and its
Preparation method carries out various modification and variations without departing from the spirit and scope of the present invention.If in this way, to of the invention these
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to encompass these changes to modifications and variations
Including modification.
Claims (10)
1. a kind of electrode material for being crosslinked the mesoporous silicon particle of carbon coating, is formed, feature by being covered with carbon on porous silicon particle
It is:
The porous silicon particle is mesoporous silicon particle, and the partial size of the mesoporous silicon particle is 0.2-5 μm, mesoporous aperture thereon
For 2-50nm；
Weight ratio between the mesoporous silicon particle and carbon is 100:1-30, and the weight ratio is the mesoporous silicon of 100:1-30
The surface cladding of grain is crosslinked with carbon；
The specific surface area for the mesoporous silicon particle that the surface cladding is crosslinked with carbon is 20-100m2/g。
2. it is according to claim 1 crosslinking the mesoporous silicon particle of carbon coating electrode material, it is characterized in that mesoporous silicon particle with
Weight ratio between carbon is 100:4-20.
3. the preparation method of the electrode material of the mesoporous silicon particle of carbon coating, including ball-milling method are crosslinked described in a kind of claim 1,
It is characterized in that steps are as follows for completion:
Step 1, first aluminium, the alusil alloy that silicon weight percent is 60-10wt%:40-90wt% are crushed, then place it in ball
In grinding machine, liquid phase ball milling is carried out according to the ratio that ratio of grinding media to material is 40-10:1, liquid-to-solid ratio is 1-10mL/g, obtaining partial size is 0.2-5
μm alusil alloy powder；
Step 2, the ratio for being first 1:1-2 according to the weight ratio of alusil alloy powder, the acid solution of 1-5mol/L, the two is placed in
At least 4h is mixed at 35-45 DEG C, obtains mesoporous silicon particle, according still further to mesoporous silicon particle, cationic surfactant and has
The weight ratio of machine carbon source solution is the ratio of 1:0.01-0.001:2-5, is mixed dry after at least 2h by three, obtains
Between product；
Step 3, intermediate product is placed in reducing atmosphere, at least 2h is calcined at 500-900 DEG C, crosslinking carbon coating is made and is situated between
The electrode material of hole silicon particle.
4. the preparation method of the electrode material of the crosslinking mesoporous silicon particle of carbon coating according to claim 3, it is characterized in that ball
Grinding jar and the material of abrading-ball are the mixture of one or more of agate, zirconium oxide, stainless steel, corundum.
5. the preparation method of the electrode material of the crosslinking mesoporous silicon particle of carbon coating according to claim 3, it is characterized in that ball
The liquid phase medium of mill is the mixture of one or more of ethyl alcohol, methanol, polyglycols, N-Methyl pyrrolidone, kerosene.
6. the preparation method of the electrode material of the crosslinking mesoporous silicon particle of carbon coating according to claim 3, it is characterized in that sour
Solution is one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, glacial acetic acid solution, phosphoric acid solution, liquor ferri trichloridi or two
Kind or more mixture.
7. the preparation method of the electrode material of the crosslinking mesoporous silicon particle of carbon coating according to claim 3, it is characterized in that positive
Ionic surface active agent is polyetherimide, polyetheramine, dopamine, laurylamine hydrochloride, lauryl amine, octadecylamine, quaternized
Polyethyleneimine, tertiary amine polyethyleneimine, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, hexadecane
Base trimethyl ammonium chloride, polyethyleneimine, in dodecyl dimethyl benzyl ammonium chloride, cetalkonium chloride
One or more kinds of mixtures.
8. the preparation method of the electrode material of the crosslinking mesoporous silicon particle of carbon coating according to claim 3, it is characterized in that having
Machine carbon source solution is sucrose solution, glucose solution, chitosan solution, starch solution, polyvinylpyrrolidonesolution solution, polypropylene
The mixture of one or more of nitrile solution, citric acid solution, phenol resin solution, polyglycol solution.
9. the preparation method of the electrode material of the crosslinking mesoporous silicon particle of carbon coating according to claim 3, it is characterized in that dry
Dry temperature is 100-200 DEG C, time 2-4min.
10. the preparation method of the electrode material of the crosslinking mesoporous silicon particle of carbon coating according to claim 3, it is characterized in that also
Originality atmosphere is the mixed of one or more of hydrogen atmosphere, nitrogen atmosphere, argon atmosphere, helium atmosphere, neon atmosphere
Close atmosphere.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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