CN105705460A - Method for preparing hollow silicon spheres as well as hollow silicon spheres prepared therefrom - Google Patents
Method for preparing hollow silicon spheres as well as hollow silicon spheres prepared therefrom Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
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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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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Provided are a method for preparing hollow silicon spheres, the hollow silicon spheres prepared therefrom, as well as an anode material, a negative electrode and a lithium ion battery using the hollow silicon spheres. The method comprises: using nano particles as template, silicon coating layer being formed on the nano particles using a silicon source by means of chemical vapor deposition, followed by template removal and purification.
Description
Technical field
The present invention relates to field of lithium ion battery。In particular it relates to the purposes of a kind of method, the hollow silicon ball thus obtained and anode material as lithium ion battery thereof preparing hollow silicon ball。
Background technology
The capacity of the graphitic anode material of existing commercial Li-ion batteries is close to its theoretical value (372mAh/g), and this is by limiting lithium ion cell application in electric automobile, energy storage and intelligent grid field。Silicon is considered as promising graphite succedaneum because it have high power capacity (～4200mAh/g, than graphite high more than 10 times in) and rich reserves。
Although silicon has high power capacity, but its shortcoming is in that capacity attenuation is fast, and this embeds and change in volume produced huge in deintercalation process mainly due to lithium。Recent studies have shown that, by designing hollow structure, the cycle performance of silica-base material can be effectively improved, described hollow structure provides reserved volume to adapt to the expansion (NanoLett.2011 during material circulation, 11,2,949 2954, Angew.Chem.Int.Ed.2012,51,2409-2413)。At one section of document (Ref.1, NanoLett.2011,11,2,949 2954) in, nano silicon masterplate by drop coating at stainless steel lining at the bottom of on, on nano silicon masterplate, prepare the silicon hollow nanospheres being interconnected again through chemistry of silicones vapour deposition (CVD)。At another section of document (Ref.2, Angew.Chem.Int.Ed.2012,51, in 2409-2413), cetyl trimethylammonium bromide (CTAB) is used to produce hole as surfactant, polystyrene (PS) nano-particle is used to produce hollow structure as template, again through the hollow porous SiO that magnesiothermic reduction obtains2Nano-particle, finally by coated with silver, to reach certain electric conductivity。
Solve the technical problem that
Although the hollow silicon ball of preparation improves cycle performance in the studies above, but its industrialized production still critical constraints。
In above-mentioned document 1, crucial drop coating process is considerably complicated and efficiency is low。In order to form uniform coating, it is necessary to be distributed in alcohol solvent by Colloidal Nanosize Silica Template, before drop coating, substrate needs to carry out oxygen plasma treatment；In drop coating process, operation needs strictly to be controlled, and the solvent evaporated is not environmentally。Even if being repeated several times by drop coating process, final silicon mass loading also only has 0.1-0.2mg/cm2, this is still too low for business application。
In above-mentioned document 2, it is relatively costly that ctab surface activating agent and Ag modifiy, and technique is cumbersome, it is difficult to realizes large-scale production。
Consider building-up process and the high cost of complexity above-mentioned, it is necessary to low cost, simple and eco-friendly synthetic method prepare hollow silicon ball。
Summary of the invention
In the present invention, hollow silicon ball (HSS) of anode material as the lithium ion battery with high power capacity and good stability has been synthesized by simple and low cost method。
According to an aspect of the invention, it is provided the method for the preparation hollow silicon ball of a kind of simple and low cost。Specifically, the method for the preparation hollow silicon ball of the present invention may be summarized as follows:
Using nano-particle as masterplate, utilize silicon source to form silicon coating on described nano-particle by chemical vapour deposition (CVD), then remove template and be purified。
According to another aspect of the present invention, it is provided that by the hollow silicon ball that the method for the present invention obtains。
According to another aspect of the present invention, it is provided that comprise the anode material of the hollow silicon ball of the present invention。
According to another aspect of the present invention, it is provided that comprise the negative pole for lithium ion battery of described anode material。
According to another aspect of the present invention, it is provided that comprise the lithium ion battery of described negative pole。
Accompanying drawing explanation
Fig. 1 shows Representative synthetic procedures and the final products HSS of the hollow silicon ball of the present invention。
Fig. 2 shows the TEM image of commercially available nano-calcium carbonate particles (20-100nm)。
Fig. 3 a, 3b show the TEM image of the HSS-1 that embodiment 1 obtains。Fig. 3 c shows the SAED pattern of HSS-1。
Fig. 4 shows SEM image and the EDS pattern of HSS-1。
Fig. 5 shows N2 adsorption/desorption isotherm and the pore-size distribution of HSS-1。
Fig. 6 shows the XRD figure spectrum of HSS-1。
Fig. 7 (a) shows Si2p spectrum (b) that XPS figure, Fig. 7 (b) of HSS-1 show HSS-1。
Fig. 8 shows the TEM image of HSS-2。
Fig. 9 shows the SEM image of HSS-2。
Figure 10 shows the XRD figure case of HSS-2。
Figure 11 shows the particle size distribution of HSS-2。
Figure 12 is shown under 400mA/g, (in first three circulation 100mA/g), the cyclic curve of HSS-1 between 0.02V and 1.5V。
Figure 13 is shown under 400mA/g, (in first three circulation 100mA/g), the cyclic curve of HSS-2 between 0.02V and 1.5V。
Detailed description of the invention
In this application, unless otherwise indicated, all percentage ratios (%) are all referring to percentage by weight。All about in the description of numerical range, statement " in the scope of A-B " and " between A and B " includes more than A and the numerical value less than B and A and B itself。
The invention discloses anode material of hollow silicon ball of lithium ion battery for having high power capacity and good circulation stability and preparation method thereof。
Compared with traditional Si powder, owing to hollow structure designs, the HSS material of the present invention shows high power capacity and good stability。The volumetric expansion that central hole structure is during lithium embeds leaves sufficient space, and the migration for electronics that is interconnected of silicon ball provides conductive network。
Relative to aforementioned documents 1, the method for the present invention simply and readily controls。Templating nanoparticles is directly used in silicon CVD, without drop coating on specific substrate。The more important thing is, with the low activity material load (0.1-0.2mg/cm in document 12) compare, it is easily achieved 0.2 to 1.5mg/cm in the method for the invention2Between active substance load, and by control coating procedure active substance load can be further increased to 3mg/cm2。
Compared with aforementioned documents 2, the synthetic method cost of the present invention is low, without expensive reactant (surfactant, silver)。Masterplate nano-particle in the inventive method can be commercially available at lower cost。Therefore, the method for the present invention has very big potentiality in industry practical application。
The preparation of HSS material
It is used as the nano-particle of template in the present invention selected from carbonate and oxide。Described carbonate is preferably selected from calcium carbonate, magnesium carbonate, strontium carbonate, brium carbonate。Described oxide is preferably selected from Al2O3, MgO, ZnO and SiO2。
It is used as the size of nano-particle of template in the present invention in the scope of 10nm to 100nm。
The silicon source used in the present invention is selected from high purity silane, chlorosilane etc.。Multiple chlorosilane can be used in the present invention, it is preferable that trichlorosilane。
The chemical vapour deposition (CVD) (CVD) adopted in the present invention is routine techniques。CVD can be briefly described as entering reative cell by current-carrying gas with the source steam of one or more gases, chemical change occurs on the surface of a substrate, and goes out required solid matter at deposited on substrates。For the present invention, in CVD process, nano-particle is placed in horizontal pipe furnace or fluid bed furnace as substrate, then by siliceous deposits to this substrate。
The particle diameter of the nano-particle used in the present invention can in the scope of 10nm to 100nm, it is preferable that in the scope of 40nm to 80nm。
In preferred embodiments, before temperature reaches 400 DEG C-500 DEG C, introduce 5%H with flow velocity 120 standard cubic centimeters per minute2With the mixture of 95% noble gas such as argon to form reducing atmosphere。Then, carry, by the noble gas of such as argon, high purity silane that purity is 99.999% and enter temperature in the stove of 400 DEG C-500 DEG C 1 hour-3 hours with the speed within the scope of 80-120 standard cubic centimeters per minute。The mixed weight ratio of silane and argon is in the scope of 10:80-2:98, it is preferred to 5:95。
In chemical vapor deposition processes, at identical temperature and flow velocity, the silicon coating of different-thickness can be obtained by controlling sedimentation time。Such as, being 450 DEG C in temperature, when flow velocity is 100 standard cubic centimeters per minute, sedimentation time is 1.5 hours, obtains the silicon coating that thickness is about 10nm；It is 2 hours between when deposited, obtains the silicon coating that thickness is about 16nm。
After reaction, in cooling procedure, in stove, pass into 5%H again2Admixture of gas with 95%Ar。
In subsequent treatment, the acid adopting concentration to be such as 2 weight % removes nano-particle to obtain the material of hollow structure。Those skilled in the art can select suitable acid for this process, as long as acid can be reacted to form soluble-salt or gas with nanoparticle template and not affect the character of silicon。Such as, based on general knowledge known in this field, described acid can be appropriately selected from hydrochloric acid, sulphuric acid and Fluohydric acid.。Those skilled in the art will know that these acid are likely to not be suitable for the template of above-mentioned all kinds。Such as, when using SiO2During as template, Fluohydric acid. is applicable, but Fluohydric acid. is not suitable for other templates。
Furthermore, it is contemplated that the oxidation of silicon in deposition process and acid treatment process, the Fluohydric acid. that working concentration is such as 10 weight % carries out purifying products, thus obtaining end product hollow silicon ball。
The hollow space size of hollow silicon ball is in the scope of 10-90nm, and the size range of primary granule is 80-100nm, and the size range of second particle is 1-30 μm, and the thickness of silicon wall is about 9-17nm。
In the present invention, term " primary granule " refers to that the primary granule of hollow silicon ball, term " second particle " refer to the granule reunited by the primary granule of hollow silicon ball。
The assembling of button cell
According to another aspect of the present invention, it is provided that a kind of anode material for lithium ion battery, it includes hollow silicon ball material, conductive agent and binding agent。
Being preferably based on the gross weight of anode material, described anode material includes the binding agent of the hollow silicon ball of 50 weight %-80 weight %, the conductive agent of 5 weight %-20 weight % and 5 weight %-30 weight %。
Described hollow silicon ball is the hollow silicon ball according to the present invention。
Those skilled in the art can select conductive agent to improve electric conductivity。Such as, above-mentioned conductive agent can be selected from conductive black, CNT and Graphene。
Described binding agent is preferably polyacrylic acid (PAA), it is also possible to selected from the mixture of sodium carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose and butadiene-styrene rubber (SBR), and Na-alginate (SA)。
As an example, based on the gross weight of anode material, described anode material includes the polyacrylic acid of the hollow silicon ball according to the present invention of 60 weight %, the conductive black of 20 weight % and 20 weight %。
In one embodiment, by the hollow silicon ball of the present invention, conductive black and polyacrylic acid according to weight ratio be 60:20:20 disperse in deionized water, to form the anode material of pulp-like。Such as, the anode material of pulp-like is poured on the Copper Foil of horizontal positioned, carries out film with the wet film applicator being preferably 150 μm and make electrode。After film, electrode is dried naturally。Then under the pressure of such as 8MPa, carry out tabletting process。After tabletting, put the electrodes in vacuum drying oven overnight dry under being preferably the temperature of 80 DEG C, ultimately form negative pole。Negative pole as formed above and lithium paper tinsel can be collectively formed the electrode pair of lithium ion battery。The 1mol/LLiPF that volume ratio can be used to be 1:1:16/ EC:DMC:EMC is as electrolyte, using the VC of 2 weight % as additive。EC is ethylene carbonate, and DMC is dimethyl carbonate, and EMC is Ethyl methyl carbonate, and VC is vinylene carbonate。Battery mould is such as 2025 type button cells。Thus make button cell。
The payload of active substance refers to the amount of the anode material being coated on Copper Foil。
For measuring the chemical property of button cell, button type battery carries out constant current charge-discharge test。Electric current density is 100mA/g (3 times circulation) and 400mA/g (following cycle), and voltage range is set to 0.02-1.5V。Weight based on the hollow silicon ball in anode calculates capacity。
Constant current charge-discharge test shows, utilizes the initial discharge capacity of the button cell that the hollow silicon ball of the present invention obtains can reach 3063mAh/g, and initial charge capacity can reach 2246mAh/g, and Initial Coulombic Efficiencies can reach 82%。Circulating through 100 times under 400mAh/g, reversible capacity still can reach 1150mAh/g。
Embodiment
The preparation of embodiment 1 hollow silicon ball HSS-1
Selecting the EV-E-006 that Ai Wei nanometer of Hefei Science and Technology Ltd. produces as nano-calcium carbonate template, its particle diameter is 50-80nm。To the horizontal pipe furnace (internal diameter is 60mm) of 450 DEG C, chemical vapour deposition (CVD) is carried out in heating。Before temperature reaches 450 DEG C, in stove, introduce the mixture of 5% hydrogen and 95% argon to form reducing atmosphere and to eliminate residual oxygen。Then, carry, by argon, the high purity silane that purity is 99.999%, with in the horizontal pipe furnace of the speed of 100 standard cubic centimeters per minute entrance temperature 450 DEG C 1.5 hours。Silane is decomposed into silicon grain and hydrogen, and silicon grain finally be deposited on nano-calcium carbonate。The mixed weight of silane and argon is than for 5:95。After deposition, the mixture of 5% hydrogen and 95% argon is introduced back in stove to accelerate cooling and to avoid silicon grain to aoxidize。In subsequent treatment, the hydrochloric acid of 2 weight % is adopted to remove nano-calcium carbonate to obtain the material of hollow structure。Considering to be likely to oxidized at deposition process silicon atom, adding the Fluohydric acid. of 10 weight % with purified product, thus obtaining end product hollow silicon ball HSS-1。
The typical pattern display HSS-1 of the HSS-1 in Fig. 3 a, 3b is made up of the hollow ball of the primary particle size narrowly distributing interconnected。The wall thickness of hollow ball is about 9-12nm。SAED pattern displaying HSS-1 in Fig. 3 c is almost amorphous materials。This is also confirmed by the X-ray diffraction pattern of Fig. 6。Fig. 6 does not show the characteristic peak of obvious crystalline silicon。
SEM image in Fig. 4 and EDS pattern displaying, except C, Si and O, are absent from impurity element in HSS material, and this also is schemed to confirm by the XPS of Fig. 7。It addition, Si2p spectrum display, the symmetrical peak centered by 99.4eV is considered Si-Si bond, and this shows that the principal states in material is elemental silicon。
Fig. 5 shows N2 adsorption/desorbing and the pore-size distribution of HSS-1。It can be seen that the specific surface area of hollow silicon ball HSS-1 and pore volume respectively 35.7m2/ g and 0.274cm3/ g。Corresponding to the pore-size distribution of size of hollow space of HSS-1 mainly between 10nm and 90nm, this is similar to the size of described nano-calcium carbonate template。
The preparation of embodiment 2 hollow silicon ball HSS-2
Embodiment 2 is roughly the same with embodiment 1, is distinctive in that the time that chemical vapour deposition (CVD) carries out is 2 hours。That is, in chemical vapor deposition processes, argon carries the high purity silane that purity is 99.999%, continues 2 hours in the horizontal pipe furnace (internal diameter is for 60mm) that the speed entrance temperature of 100 standard cubic centimeters per minute is 450 DEG C。
The typical pattern display HSS-2 of the HSS-2 in Fig. 8 is mainly made up of the hollow ball of the primary particle size narrowly distributing interconnected。The wall thickness of hollow ball is about 16nm。
The X-ray diffraction pattern of Figure 10 confirms that HSS-2 material is also unbodied, because not showing the characteristic peak of obvious crystalline silicon。
SEM image display HSS-2 in Fig. 9 has secondary chondritic。The adjoining dimensions of primary particle size and nano-calcium carbonate, the particle diameter of its second particle is about 10 μm, consistent with the particle size distribution measurement result of display in Figure 11。Figure 11 shows that the particle size range of the hollow silicon ball of about 95% is 1-30 μm。
The assembling of embodiment 3 button cell 1
The hollow silicon ball HSS-1 adopting embodiment 1 preparation prepares negative pole。Anode material includes the binding agent of the hollow silicon ball of 60 weight %, the conductive carbon black of 20 weight % and 20 weight %, and wherein binding agent is polyacrylic acid (PAA)。The negative pole formed is constituted together with lithium paper tinsel the electrode pair of lithium ion battery。Volume ratio is the 1mol/LLiPF of 1:1:16/ EC:DMC:EMC is as electrolyte, and the VC of 2 weight % is as additive。Battery mould is 2025 type button cells, thus makes button cell。
After measured, the payload of active substance is 0.85mg/cm2。
For measuring the chemical property of button cell, button type battery carries out constant current charge-discharge test。Electric current density is 100mA/g (3 times circulation) and 400mA/g (following cycle), and voltage range is set to 0.02-1.5V。
Figure 12 shows charge-discharge performance curve。Result of the test shows, the initial discharge capacity of button cell reaches 3063mAh/g, and initial charge capacity is 2246mAh/g。Initial coulomb efficiency is 73%。Under 400mAh/g after 160 times circulate, reversible capacity still reaches 1150mAh/g。That is, after 160 circulations, capability retention is 73%。Circulating from 20 times to 160 times, capacity attenuation is less than 2%。
The assembling of embodiment 4 button cell 2
The hollow silicon ball HSS-2 adopting embodiment 2 preparation prepares negative pole。This anode material includes the binding agent of the hollow silicon ball material of 60 weight %, the conductive carbon black of 20 weight % and 20 weight %, and wherein binding agent is polyacrylic acid (PAA)。The negative pole formed is constituted together with lithium paper tinsel the electrode pair of lithium ion battery。Volume ratio is the 1mol/LLiPF of 1:1:16/ EC:DMC:EMC is as electrolyte, using the VC of 2 weight % as additive。Battery mould is 2025 type button cells, thus makes button cell。
After measured, the payload of active substance is 0.62mg/cm2。
For measuring the chemical property of button cell, button type battery carries out constant current charge-discharge test, and electric current density is 100mA/g (3 times circulation) and 400mA/g (following cycle), and voltage range is set to 0.02-1.5V。
Figure 13 shows charge-discharge performance curve。Result of the test shows, the initial discharge capacity of button cell reaches 2547mAh/g, and initial charge capacity is 2093mAh/g。Initial coulomb efficiency is 82%。Under 400mAh/g after 100 times circulate, reversible capacity still reaches 800mAh/g。Capability retention is 44%。
The foregoing describe the present invention, however, it will be apparent that, it is possible to change the present invention in many ways。These changes are not regarded as a departure from the spirit and scope of the invention, and these changes that it will be apparent to those skilled in the art that include in the scope of appended claims。
Claims (17)
1. the method preparing hollow silicon ball, comprising:
Use nano-particle as masterplate, utilize silicon source to form silicon coating on described nano-particle by chemical vapour deposition (CVD), remove described masterplate subsequently, and be purified。
2. method according to claim 1, the particle diameter of wherein said nano-particle is in the scope of 10nm to 100nm。
3. method according to claim 1 and 2, wherein said silicon source is selected from high purity silane and chlorosilane。
4. the method according to any one of claim 1-3, wherein said chemical vapour deposition (CVD) carries out 1-3 hour at the temperature of 400-500 DEG C。
5. the method according to any one of claim 1-4, the material of wherein said nano-particle is selected from carbonate and oxide。
6. method according to claim 5, wherein said carbonate is selected from calcium carbonate, magnesium carbonate, strontium carbonate and brium carbonate。
7. method according to claim 5, wherein said oxide is selected from Al2O3, MgO, ZnO and SiO2。
8. the method according to claim 6 or 7, wherein removes described nano-particle masterplate the product obtained further by Fluohydric acid. purification by acid treatment。
9. method according to claim 8, wherein depends on described masterplate, and the acid for described acid treatment is selected from hydrochloric acid, sulphuric acid and Fluohydric acid.。
10. hollow silicon ball, it is characterised in that the size of the hollow space of described hollow silicon ball is in the scope of 10-90nm, and the size of primary granule is in the scope of 80-100nm, agglomerated primary particles the size of the second particle formed is in the scope of 1-30 μm。
11. hollow silicon ball according to claim 10, it is characterised in that silicon wall is the unformed silicon that thickness is about 9-17nm。
12. anode material, comprising:
Hollow silicon ball, conductive agent and the binding agent that hollow silicon ball according to claim 10 or 11 or the method described in any one of claim 1-9 obtain。
13. anode material according to claim 12, the binding agent of the hollow silicon ball, the conductive agent of 5 weight %-20 weight % and the 5 weight %-30 weight % that obtain based on the gross weight of described anode material, it hollow silicon ball according to claim 10 or 11 including 50 weight %-80 weight % or the method described in any one of claim 1-9。
14. the anode material according to claim 12 or 13, wherein said conductive agent is selected from conductive black, CNT and Graphene。
15. according to the anode material described in any one of claim 12-14, wherein said binding agent is selected from the mixture of polyacrylic acid, sodium carboxymethyl cellulose, sodium carboxymethyl cellulose and butadiene-styrene rubber, and Na-alginate。
16. negative pole, it includes the anode material according to any one in claim 12-15。
17. lithium ion battery, it includes negative pole according to claim 16。
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| PCT/CN2013/079760 WO2015010230A1 (en) | 2013-07-22 | 2013-07-22 | Method for preparing hollow silicon spheres as well as hollow silicon spheres prepared therefrom |
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| CN112242504A (en) * | 2019-07-18 | 2021-01-19 | 北京清创硅谷科技有限公司 | Silicon carbide coated hollow silicon material, preparation method thereof, and electrode and electrochemical device using same |
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