CN106560942B - A kind of processing method of Silicon Based Anode Materials for Lithium-Ion Batteries - Google Patents
A kind of processing method of Silicon Based Anode Materials for Lithium-Ion Batteries Download PDFInfo
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- CN106560942B CN106560942B CN201610370530.4A CN201610370530A CN106560942B CN 106560942 B CN106560942 B CN 106560942B CN 201610370530 A CN201610370530 A CN 201610370530A CN 106560942 B CN106560942 B CN 106560942B
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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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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 processing methods of Silicon Based Anode Materials for Lithium-Ion Batteries.The processing method are as follows: 1) silicon powder, assistant formation material are dispersed in volatile solvent, obtain solution A;The mass percent that silicon powder accounts for raw material total amount is 5%~90%;2) acquired solution A is filtered, and drying and forming-film or club are to form combination electrode;3) combination electrode is fixed on the vibrator of electrospark impregnation machine, control operating voltage is 120~250V, and operating current is 0.1~3A, and under inert atmosphere or reducing atmosphere, using conductive plate as substrate, will be deposited on substrate after the combination electrode etching impact after refinement;4) material on base material will be deposited to scrape.Processing method provided by the invention is environmental-friendly, simple and easy to do, and yield is high, and controllability is good, is suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of processing methods of Silicon Based Anode Materials for Lithium-Ion Batteries.
Background technique
Silica-base material is considered as a kind of very promising lithium since it is up to the high-energy-density of 4200mAh/g
Ion battery cathode material, but its faced in practical applications serious problems such as charge and discharge when generate huge deformation
(300%), cycle life is low low with first circle coulombic efficiency hinders its large-scale commercial application.And the weight solved these problems
Want strategy first is that by sized nanostructures, the reason is that silicon materials can be buffered effectively when being reduced in size to nanoscale
Volume benefit simultaneously improves cycle performance.
The method for usually preparing nano-structured silica-base material be related to high temperature or rigorous process such as high temperature vapour deposition process and
Magnesium reduction process, these methods are not only at high cost, and have certain risk and a degree of environmental pollution.Therefore development green
The preparation method of environmental protection and safety seems very significant.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome the existing method for preparing nano-structured silica-base material not
But it is at high cost, and have the defect of certain risk and a degree of environmental pollution, and provide a kind of strong using electric spark
The processing method of change technology secondary operation Silicon Based Anode Materials for Lithium-Ion Batteries.
The present invention adopts the following technical solutions to solve above-mentioned technical problem:
A kind of processing method of Silicon Based Anode Materials for Lithium-Ion Batteries, it is characterized in that, the processing method includes as follows
Step:
(1) silicon powder, assistant formation material are dispersed in volatile solvent, obtain solution A;The silicon powder accounts for the original
The mass percent for expecting total amount is 5%~90%, and the raw material total amount refers to the quality sum of silicon powder and assistant formation material;
(2) acquired solution A is filtered, and drying and forming-film or club are to form combination electrode;
(3) combination electrode is fixed on the vibrator of electrospark impregnation machine, control operating voltage be 120V~
250V, operating current are 0.1A~3A, and under inert atmosphere or reducing atmosphere, using conductive plate as substrate, after refinement
It is deposited on substrate after combination electrode etching impact;
(4) material on base material will be deposited to scrape.
The principle of processing method of the invention is as follows: being that electricity is made in the non-uniform powder silicon materials of size and shape first
Pole recycles the energy of electrospark impregnation machine excitation to large-sized silicon powder material, carries out secondary add under certain atmosphere
Work refines it further, to form nano silicon material of uniform size.
In step (1), the partial size of the silicon powder is in the general category of this field, and preferably 100 μm hereinafter, be more preferably
1 μm or less.
In step (1), the assistant formation material is preferably sheet carbon material.The sheet carbon material is preferably
For graphene and/or graphite flake.The thickness of the assistant formation material is in the general category of this field, and preferably 1 μm or less.
In step (1), the method for the dispersion is conventional method in that art, preferably ultrasonic disperse.
In step (1), the volatile solvent has this field conventional sense, is preferably comprised water, methanol, second
One of alcohol, ethylene glycol, acetonitrile, ether and n-butanol are a variety of.
In step (1), the mass percent that the silicon powder accounts for the raw material total amount is preferably 50%.
In step (2), the suction filtration preferably carries out under vacuum conditions.
In step (3), the operating voltage of the electrospark impregnation machine is preferably 150V, and operating current is preferably
0.75A is hereinafter, but be not zero.
In step (3), the inert atmosphere or reducing atmosphere have this field conventional sense, preferably argon gas, or
The mixed gas of the mixed gas or nitrogen and hydrogen of nitrogen or helium or argon gas and hydrogen, is more preferably argon gas.Wherein,
The volume percent content of hydrogen is preferably 1%~40% in the mixed gas of the argon gas and hydrogen.The nitrogen and hydrogen
The volume percent content of hydrogen is preferably 1%~40% in the mixed gas of gas.
In step (3), the conductive plate has this field conventional sense, is preferably comprised metal plate, graphite plate and carbon
One of plate is a variety of, is more preferably graphite plate.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: processing method of the invention can at normal temperatures and pressures, by by size
Electrode is made in larger and particle diameter distribution unevenness powder body material, uses electrospark impregnation machine for working equipment, further to material
Refinement and uniform particle sizesization.The method of electric spark deposition process preparation nanometer silicium cathode provided by the invention is environmental-friendly, easy
Easy, yield is high, and controllability is good, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is TEM transmission electron microscope photo of the silicon power raw material used in embodiment 1 under 50000 times of amplification.
Fig. 2 is TEM transmission electricity of the obtained nano silicon material of processing method by embodiment 1 under 100000 times of amplification
Mirror photo.
Fig. 3 is grain size distribution of the silicon power raw material under 50000 times used in embodiment 1.
Fig. 4 is the grain size distribution for the nano silica-base material that the processing method of embodiment 1 obtains.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Embodiment 1
What the present embodiment was recorded is the processing side that the nano silica fume of 25~150nm wide distribution is further refined and homogenized
Method.
50mg graphene and 50mg silicon powder are weighed, they are dispensed into water by two kinds of material use ultrasonic disperses.Then
Using vacuum filtration, by two kinds of substances from being separated in aqueous solution and form membrane electrode after drying.Graphene and silicon are answered
Film is closed on electrospark impregnation machine vibration device, control work atmosphere is argon gas, after connecting electrospark impregnation electromechanical source, adjusts work
Making voltage is 150V, and current gear is 1 grade (corresponding current is 0~0.75A), uses graphite plate for substrate.By electrode slowly to base
Material is close, and when the two is close enough, the electric spark of generation, which performs etching electrode, to be impacted and deposit on graphite plate substrate.It is deposited on
Deposit on graphite plate is obtained target product.
Silicon transmission electron microscope results difference after initial silicon powder and electrospark impregnation machine secondary operation is as depicted in figs. 1 and 2.Thoroughly
The device model of radio mirror is microscope JEM-2100, acceleration voltage 200KV.The enlargement ratio of Fig. 1 is 50000 times, Fig. 2's
Enlargement ratio is 100000 times.
It can be seen from the figure that the partial size of initial silicon powder is in uneven distribution from 25nm~150nm, and pass through secondary operation
Afterwards, partial size becomes uniformly, and particle refine after average grain diameter be 25nm.
The grain size distribution of silicon power raw material is as shown in Figure 3.The nano silica-base material obtained according to the processing method of embodiment 1
Grain size distribution it is as shown in Figure 4.As can be seen that after processing method of the invention, what is obtained is received for the comparison of Fig. 3 and Fig. 4
The partial size of rice silica-base material is in normal distribution, and homogenization degree greatly improves.
Embodiment 2
95mg graphene and 5mg silicon powder are weighed, they are dispensed into ethyl alcohol by two kinds of material use ultrasonic disperses.Then
Using vacuum filtration, by two kinds of substances from being separated in aqueous solution and form membrane electrode after drying.Graphene and silicon are answered
Film is closed on electrospark impregnation machine vibration device, control work atmosphere is hydrogen/argon gas (5%), and it is electromechanical to connect electrospark impregnation
Behind source, adjusting operating voltage is 120V, and current gear is 1 grade (corresponding current is 0~0.35A), uses graphite plate for substrate.It will be electric
Pole is slowly close to substrate, and when the two is close enough, the electric spark of generation, which performs etching electrode, to be impacted and deposit to graphite plate base
On material.The deposit being deposited on graphite plate is obtained target product.The present embodiment can be refined and be homogenized journey
Spend the nano silica-base material significantly improved.
Embodiment 3
10mg graphene and 90mg silicon powder are weighed, they are dispensed into n-butanol by two kinds of material use ultrasonic disperses.
Then using vacuum filtration, by two kinds of substances from being separated in aqueous solution and form membrane electrode after drying.By graphene and
For silicon composite membrane on electrospark impregnation machine vibration device, control work atmosphere is hydrogen/nitrogen (5%), connects electrospark impregnation
After electromechanical source, adjusting operating voltage is 245V, and current gear is 1 grade (corresponding current fluctuation range is about 0~1.05A), is used
Graphite plate is substrate.Electrode is slowly close to substrate, and when the two is close enough, the electric spark of generation performs etching impact to electrode
And it deposits on graphite plate substrate.The deposit being deposited on graphite plate is obtained target product.The present embodiment can obtain
To the nano silica-base material refined and homogenization degree significantly improves.
Embodiment 4~6
It is same as Example 1 that embodiment 4~6 prepares procedure of processing used in silicon based composite material, the difference is that
Parameter described in table 1.
The parameter of 1 embodiment 4~6 of table
Embodiment 4~6 can be refined and be homogenized the nano silica-base material that degree significantly improves.
Comparative example 1
This comparative example investigate be in step (3) operating voltage of electrospark impregnation machine and operating current not in this hair
It is bright limit " operating voltage as 120V~250V, operating current is the situation in 0.1~3A " range.The result shows that voltage or
When electric current is lower than the numberical range, electric spark can not be formed;If being higher than the numberical range is easy breakdown substrate again.
Claims (11)
1. a kind of processing method of Silicon Based Anode Materials for Lithium-Ion Batteries, which is characterized in that the processing method includes following step
It is rapid:
(1) silicon powder, assistant formation material are dispersed in volatile solvent, obtain solution A;The silicon powder accounts for raw material total amount
Mass percent is 5%~90%, and the raw material total amount is the quality sum of silicon powder and assistant formation material;
(2) acquired solution A is filtered, and drying and forming-film or club are to form combination electrode;
(3) combination electrode is fixed on the vibrator of electrospark impregnation machine, control operating voltage is 120 V ~ 250V, work
Making electric current is 0.1A~3A, and under inert atmosphere or reducing atmosphere, using conductive plate as substrate, the combination electrode is etched
It is deposited on substrate after impact;
(4) material on base material will be deposited to scrape;
Wherein, in step (1), the assistant formation material is sheet carbon material, and the sheet carbon material is graphene and/or stone
Ink sheet.
2. processing method as described in claim 1, which is characterized in that in step (1), the partial size of the silicon powder be 100 μm with
Under.
3. processing method as claimed in claim 2, which is characterized in that the partial size of the silicon powder is for 1 μm hereinafter, the sheet
Carbon material with a thickness of 1 μm or less.
4. processing method as described in claim 1, which is characterized in that in step (1), described is separated into ultrasonic disperse;Institute
The volatile solvent stated includes one of water, methanol, ethyl alcohol, ethylene glycol, acetonitrile, ether and n-butanol or a variety of.
5. processing method as described in claim 1, which is characterized in that in step (1), the silicon powder accounts for the raw material total amount
Mass percent be 50%.
6. processing method as described in claim 1, which is characterized in that in step (2), the suction filtration under vacuum conditions into
Row.
7. processing method as described in claim 1, which is characterized in that in step (3), the work of the electrospark impregnation machine
Voltage is 150V, and operating current is 0.1A ~ 0.75A.
8. processing method as described in claim 1, which is characterized in that in step (3), the inert atmosphere or reducing atmosphere
For the mixed gas of the mixed gas or nitrogen and hydrogen of argon gas or nitrogen or helium or argon gas and hydrogen.
9. processing method as claimed in claim 8, which is characterized in that the body of hydrogen in the mixed gas of the argon gas and hydrogen
Product degree is 1%~40%;In the mixed gas of the nitrogen and hydrogen the volume percent content of hydrogen be 1%~
40%。
10. processing method as described in claim 1, which is characterized in that in step (3), the conductive plate be metal plate or
Carbon plate.
11. processing method as claimed in claim 10, which is characterized in that in step (3), the carbon plate is graphite plate.
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Citations (2)
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CN101849306A (en) * | 2007-09-06 | 2010-09-29 | 佳能株式会社 | Method for producing lithium ion storage/release material, lithium ion storage/release material, electrode structure using the material, and electricity storage device |
CN203333312U (en) * | 2013-05-23 | 2013-12-11 | 苏州金瑞晨科技有限公司 | Arc discharge device for preparing nanometer silicon powder |
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2016
- 2016-05-30 CN CN201610370530.4A patent/CN106560942B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101849306A (en) * | 2007-09-06 | 2010-09-29 | 佳能株式会社 | Method for producing lithium ion storage/release material, lithium ion storage/release material, electrode structure using the material, and electricity storage device |
CN203333312U (en) * | 2013-05-23 | 2013-12-11 | 苏州金瑞晨科技有限公司 | Arc discharge device for preparing nanometer silicon powder |
Non-Patent Citations (2)
Title |
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Optical properties of silicon nanoparticles synthesized via electrical spark discharge in water;Mehdi Mardanian等;《Applied Physics A》;20121116;第112卷;第437-442页 |
Silicon nanoparticles produced by spark discharge;Vincent A. Vons等;《JOURNAL OF NANOPARTICLE RESEARCH》;20110628;第13卷;第4867-4879页 |
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