CN105185970A - Silicon-coated carbon particle composite material and preparation method and equipment and application - Google Patents
Silicon-coated carbon particle composite material and preparation method and equipment and application Download PDFInfo
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- CN105185970A CN105185970A CN201510494335.8A CN201510494335A CN105185970A CN 105185970 A CN105185970 A CN 105185970A CN 201510494335 A CN201510494335 A CN 201510494335A CN 105185970 A CN105185970 A CN 105185970A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/62—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 relates to a silicon-coated carbon particle composite material, a preparation method, preparation equipment and an application. Nanometer silicon is prepared by reaction and decomposition of low-temperature plasmas; a product can be prepared by chemical vapor deposition under an ambient temperature condition to prepare a carbon particle coated with an amorphous silicon layer; the size of the nanometer silicon particle can be further effectively regulated and controlled through adjustment of reaction air flow and reaction power; the size can be freely controlled within the range of 5-1,000nm; and a chemical vapor deposition chamber is designed into a rotating mode, so that the compound uniformity of the nanometer silicon and a base can be effectively improved; and furthermore, a silicon layer with a controllable thickness can be obtained by controlling the conditions such as the chemical vapor deposition rate, the rotation rate and the like.
Description
Technical field
The present invention relates to the preparation field of nano silicon material and lithium ion battery negative material, particularly relate to a kind of carbon granule composite material of coated Si, preparation method and equipment and purposes.
Background technology
Lithium ion battery is the ideal source of portable electric appts, electric automobile and energy-storage system, exploitation specific energy is high, fail safe good and new electrode materials with low cost is the core content of Study on Li-ion batteries development field, and the development of research to lithium ion battery of new generation of Novel anode material is significant.
The lithium ion battery negative material of current maturation is mainly graphite type material, and its theoretical specific capacity is only 372mAh/g, and development potentiality is limited, cannot meet the demand of following lithium ion battery to high-energy-density.Research find as Al, Sn, Sb, Si etc. can with Li alloyed metal (AM) and alloy type material thereof, its reversible lithium storage capacity is far longer than graphite negative electrodes, if the theoretical capacity of Si negative pole is up to 4200mAh/g, but such negative material removal lithium embedded volumetric expansion is shunk comparatively large (>300%), high bulk effect causes poor cyclical stability, makes these system distance degrees of being practical still there is certain distance.
In order to improve the cycle performance of silicium cathode; those skilled in the art can improve the Volumetric expansion of silicon materials usually by the compound of the alloying of the nanometer of silicon, silicon and metal, silicon and material with carbon element; wherein the composite material of nano-silicon and graphite has larger application prospect, and the synthesis of nano-silicon and dispersed in graphite matrix are key technologies.
CN101527357B discloses a kind of method that silicon-carbon composite cathode material is prepared in pyrolysis, and use nano-silicon as kernel, organic cracking forms amorphous carbon coating layer, prepares the nano-silicon/amorphous carbon composite negative pole material of nucleocapsid structure.CN104332621A discloses a kind of method preparing hollow Nano silicon structure, utilizes metallothermic reduction silicon dioxide, prepares silicon nanoparticle, then by the non-zinc oxide-silicon dioxide in acid etch inside, obtains hollow nano silicon ball.These two kinds of methods do not solve the dispersed problem of nano-silicon and graphite base, and the comparatively loaded down with trivial details and bad control of preparation process.
CN102214817A discloses a kind of carbon/silicon/carbon nano composite structure cathode material and preparation method thereof, by chemical vapor deposition method depositing nano silicon on carbon base body, then by chemical vapor deposition method in nano-silicon Surface coating nano-sized carbon; Carbon matrix material is porous carbon, carbon nano-tube or Graphene.The hole of common porous carbon materials (as active carbon) is less, be difficult to effectively carry nano silicon material, and carbon nano-tube or Graphene self is easily reunited, and are also difficult to realize the uniform deposition of nano silicon material on its surface.
Therefore, how simple and effective prepare the controlled nano-silicon of particle size uniformity, and make itself and the even compound of material with carbon element, be that field of lithium ion battery needs the technical barrier that will solve badly.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is the preparation method of the carbon granule composite material providing a kind of coated Si, and described method comprises the steps:
(1) granular graphite is placed in inductance coupling high-CVD (Chemical Vapor Deposition) chamber;
(2) the plasma reaction district of silicon source reaction gas to inductance coupling high-CVD (Chemical Vapor Deposition) chamber is passed into, in vacuum atmosphere, silicon source is decomposed, under inductance coupling high-CVD (Chemical Vapor Deposition) chamber rotating condition, carry out chemical vapour deposition (CVD), obtain the graphite granule of Surface coating silicon;
(3) by the graphite granule of Surface coating silicon through grinding, screening, obtain the carbon granule composite material of Surface coating silicon.
Using plasma of the present invention strengthens chemical vapour deposition (CVD) mode, low-temperature growth nanometer silicon composite material; And by rotary type tube furnace, at granular carbon material surface Dynamic deposition silicon, obtain the carbon granule composite material of coated Si.The present invention improves the compound uniformity of nano-silicon and carbon granule substrate by the mode rotating compound.Method provided by the invention is simple, easy suitability for industrialized production, and the carbon granule composite material of the coated Si prepared has high power capacity, the high feature such as efficiency, long-life first.
The average grain diameter of granular graphite of the present invention is 5 ~ 25 μm, such as 6 μm, 8 μm, 13 μm, 18 μm, 22 μm etc.
Preferably, described silicon source is selected from SiH
4, Si
2h
6, Si
3h
8, SiCl
4, SiHCl
3, Si
2cl
6, SiH
2cl
2or SiH
3the combination of any a kind or at least 2 kinds in Cl.
Preferably, the carrier gas of described silicon source reaction gas is the combination of any a kind or at least 2 kinds in argon gas, hydrogen or nitrogen.
Preferably, in the reaction gas of described silicon source, the concentration in silicon source is 5 ~ 80v%, such as 7v%, 20v%, 32v%, 45v%, 58v%, 63v%, 75v%, 78v% etc.
Preferably, the speed that passes into of described silicon source reaction gas is 5 ~ 100sccm, such as 8sccm, 15sccm, 35sccm, 58sccm, 75sccm, 88sccm, 96sccm etc.
Preferably, the temperature that passes into of described silicon source reaction gas is 25 ~ 100 DEG C, such as 30 DEG C, 38 DEG C, 50 DEG C, 65 DEG C, 78 DEG C, 88 DEG C, 95 DEG C etc.
Preferably, the power of described inductance coupling high is 50 ~ 350W, such as 60W, 80W, 120W, 150W, 180W, 230W, 280W, 310W, 340W etc.
Preferably, the temperature of described chemical vapour deposition (CVD) is 25 ~ 900 DEG C, such as 30 DEG C, 40 DEG C, 100 DEG C, 300 DEG C, 500 DEG C, 600 DEG C, 800 DEG C etc., preferably 25 ~ 60 DEG C or 700 ~ 800 DEG C, obtain the carbon granule composite material of coated amorphous silicon when chemical vapour deposition (CVD) temperature is 25 ~ 60 DEG C, obtain the carbon granule composite material of coated crystalline silicon when chemical vapour deposition (CVD) temperature is 700 ~ 800 DEG C.
Preferably, the rotating speed of described rotation is 1 ~ 10 rev/min, such as 3 revs/min, 5 revs/min, 8 revs/min etc.
In the preparation method of the carbon granule composite material of coated Si of the present invention, silicon source concentration in the reaction gas of silicon source, the reaction temperature passing into speed and CVD (Chemical Vapor Deposition) chamber, inductance coupling high power are all relevant with the speed of chemical vapour deposition (CVD), and the speed of the rotary speed of CVD (Chemical Vapor Deposition) chamber, chemical vapour deposition (CVD) and the Time dependent coated uniformity of carbon granule surface silicon layer.The present invention carries out chemical vapour deposition (CVD) under 25 ~ 60 DEG C of conditions can obtain amorphous silicon layer.
Two of object of the present invention is the equipment of the preparation method providing a kind of carbon granule composite material for coated Si as described in one of object, and described equipment comprises:
I () CVD (Chemical Vapor Deposition) chamber, for depositing silicon on carbon particles;
(ii) plasma generator, for generation of plasma; Described plasma generator comprises radio-frequency power supply, and with the inductance-coupled coil of radio-frequency power supply Electricity Federation, described inductance-coupled coil uniform winding is outside CVD (Chemical Vapor Deposition) chamber;
(iii) gas supply system, for supplying silicon source reaction gas to CVD (Chemical Vapor Deposition) chamber;
(iv) vacuum system, for providing the vacuum of CVD (Chemical Vapor Deposition) chamber;
V () drive unit, horizontally rotates for driving CVD (Chemical Vapor Deposition) chamber.
The equipment of the preparation method of the carbon granule composite material for coated Si provided by the invention arranges drive unit and horizontally rotates for driving CVD (Chemical Vapor Deposition) chamber, thus Dynamic deposition, the carbon granule composite material of the coated Si had good uniformity.
Preferably, described equipment also comprises (vi) exhaust collection treatment system, and process for the tail gas collecting generation, it comprises the cold-trap by cooled with liquid nitrogen, and described cold-trap is connected with chemical gas-phase deposition system gas outlet.Exhaust collection treatment system effectively can avoid the pollution to environment and the corrosion to vacuum equipment.
Preferably, between described cold-trap and chemical gas-phase deposition system gas outlet, metal screen is set;
Preferably, the order number of described metal screen is 200 ~ 500 orders, preferably 200 orders, 325 orders or 500 orders.
Described metal screen can effective block carbon particle, avoids it on the impact of vacuum equipment.
Described CVD (Chemical Vapor Deposition) chamber is quartz ampoule, and described quartz ampoule downstream direction comprises air inlet section, sample placement section and air outlet section; Described sample placement section is larger than the caliber of air inlet section and air outlet section.
Preferably, the internal diameter of the quartz ampoule of described air inlet section and air outlet section is 4 ~ 5cm, such as 4.3cm, 4.6cm, 4.8cm etc.; Preferred described air inlet section is identical with the internal diameter of the quartz ampoule of air outlet section.
Preferably, the internal diameter of described sample placement section is 1.4 ~ 2 times of air inlet section internal diameter, such as 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times etc.
Preferably, the length of described sample placement section is 10 ~ 30cm.
The sample placement section of described quartz ampoule arranges at least one piece of baffle plate, and described baffle plate is arranged along axis in the shape of a spiral at quartz ampoule inwall, and the hand of spiral is identical with the direction of rotation of CVD (Chemical Vapor Deposition) chamber; The spiral starting point of described baffle plate is arranged at 1/3 ~ 1/2 place of CVD (Chemical Vapor Deposition) chamber;
Preferably, described height of baffle plate is 0.2 ~ 0.5 times of described sample placement section internal diameter, such as 0.3 times, 0.4 times, 0.5 times etc.
Preferably, described baffle length is 0.2 ~ 0.5 times of described sample placement section length, such as 0.3 times, 0.4 times, 0.5 times etc.
Preferably, described baffle plate is straight plate or wave-shape board, preferred wave-shape board;
Preferably, described baffle plate number is 3 ~ 6 pieces, and every block baffle plate spiral starting point is evenly distributed on the interior cross section of quartz tube sample placement section, and on same circumference.
The caliber of quartz tube sample placement section is set to large compared with the caliber of air inlet section and air outlet section by the present invention, effectively can extend the time of staying of granular graphite in CVD (Chemical Vapor Deposition) chamber, prevent from flowing out with air-flow at granular graphite.Further, the present invention, by the structure of baffle plate and the concrete setting of arrangement, more effectively can extend the time of staying of granular graphite in CVD (Chemical Vapor Deposition) chamber, improves the speed of reaction, and the deposition uniformity of silicon layer.
Inductance-coupled coil of the present invention is made up of hollow copper tubing.
Preferably, described hollow copper tubing inside is connected with cooling fluid.
Preferably, described cooling fluid is cooling water.
Gas supply system of the present invention is at least 1 air inlet pipe be connected with CVD (Chemical Vapor Deposition) chamber air inlet, preferably 3 ~ 5 air inlet pipe.
Preferably, described air inlet pipe can control feed rate.
Preferably, in described gas supply system, tracing system is set, with control temperature at 25 ~ 100 DEG C.
Drive unit of the present invention comprises the rotating shaft providing the rotation motor of power and rotated by rotation motor, and described rotating shaft is fixedly connected with the quartz ampoule of CVD (Chemical Vapor Deposition) chamber.
Three of object of the present invention is to provide a kind of carbon granule composite material of the coated Si that method prepares as described in one of object, and described composite material is the silicon layer of carbon granule external sheath non crystalline structure, or the silicon layer of carbon granule external sheath crystal structure.
Preferably, as the described chemical vapour deposition (CVD) temperature < of claim 1 step (2) 600 DEG C, the composite material of non crystalline structure silicon carbon coated particle is obtained;
Preferably, when described chemical vapour deposition (CVD) temperature >=650 DEG C of claim 1 step (2), the composite material of crystal structure silicon carbon coated particle is obtained;
Preferably, the particle diameter of the carbon granule composite material of described coated Si is 5 ~ 1000nm, such as 8nm, 18nm, 50nm, 180nm, 240nm, 380nm, 700nm, 850nm, 980nm etc.
Four of the object of the invention is to provide a kind of using method of carbon granule composite material of coated Si as described in three of object, and the carbon granule composite material of described coated Si is used for lithium ion battery negative material.
Preferably, the content of carbon granule composite material in lithium ion battery negative material of described coated Si is 0.1 ~ 100wt%, preferably 0.5 ~ 60wt%, further preferred 1 ~ 30wt%.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention use reaction of low temperature plasma decompose prepare nano-silicon, can under normal temperature (25 ~ 60 DEG C) condition chemical vapour deposition (CVD) preparing product, obtain the carbon granule of coated amorphous silicon layer; Be further advanced by the adjustment of reaction gas flow speed, reaction power, silicon nanoparticle size can be regulated and controled, freely can control within the scope of 5 ~ 1000nm;
(2) the present invention is by the change of CVD (Chemical Vapor Deposition) chamber temperature, controls the crystalline state of silicon in composite material; Amorphous nano silicon can be obtained under low temperature (<600 DEG C) condition, crystalline state nano-silicon can be obtained under high temperature (>=650 DEG C) condition;
(3) by CVD (Chemical Vapor Deposition) chamber is designed to rotation mode, the uniformity of nano-silicon and substrate compound can effectively be improved; Further, by the controlled silicon layer of thickness can be obtained to the control of the conditions such as chemical vapour deposition (CVD) speed, the speed of rotation.
(4) the present invention is large compared with the caliber of air inlet section and air outlet section by being set to by the caliber of quartz tube sample placement section, effectively can extend the time of staying of granular graphite in CVD (Chemical Vapor Deposition) chamber, prevent from flowing out with air-flow at granular graphite; Further, the present invention passes through the structure of baffle plate and the concrete setting of arrangement, it is as wavy in baffle plate is arranged to, baffle plate is set to helical form, and concrete height of baffle plate etc., with baffle plate in arrangement circumferentially, all to obtaining the longer time of staying of granular graphite in CVD (Chemical Vapor Deposition) chamber, the uniformity improving reaction speed and silicon layer further all has positive role.
Accompanying drawing explanation
The structural representation of the equipment of the carbon granule composite material for the preparation of coated Si that Fig. 1 provides for apparatus embodiments 2; 100 CVD (Chemical Vapor Deposition) chamber; 101 quartz tube sample placement section; 102 quartz ampoule air inlet section; 103 quartz ampoule air outlet section; 200 plasma generators; 201 inductance-coupled coils; 202 radio-frequency power supplies; 300 gas supply systems; 301 air inlet pipe; 302 tracing systems; 400 vacuum systems; 600 exhaust collection treatment systems, 601 metal filter screens;
Fig. 2 is the inwall deployed configuration schematic diagram in axial direction of chemical vapour deposition (CVD) quartz ampoule 100 in apparatus embodiments 2; 104 baffle plates;
Fig. 3 is the scanning electron microscope image that Application Example 1 obtains the carbon granule composite material of coated Si;
Fig. 4 is the X ray diffracting spectrum of illustrative examples 1 gained silicon nanoparticle;
Fig. 5 is the scanning electron microscope image of illustrative examples 1 gained silicon nanoparticle;
Fig. 6 is the scanning electron microscope image of illustrative examples 2 gained silicon nanoparticle;
Fig. 7 is the X-ray diffractogram of illustrative examples 3 gained silicon nanoparticle.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Apparatus embodiments 1 provides a kind of equipment of the carbon granule composite material for the preparation of coated Si, and described equipment comprises:
I () CVD (Chemical Vapor Deposition) chamber 100, for depositing silicon on carbon particles;
(ii) plasma generator 200, for generation of plasma; Described plasma generator comprises radio-frequency power supply 202, and with the inductance-coupled coil 201 of radio-frequency power supply Electricity Federation, described inductance-coupled coil uniform winding is outside CVD (Chemical Vapor Deposition) chamber;
(iii) gas supply system 300, for supplying silicon source reaction gas to CVD (Chemical Vapor Deposition) chamber;
(iv) vacuum system 400, for providing the vacuum of CVD (Chemical Vapor Deposition) chamber;
V () drive unit, horizontally rotates for driving CVD (Chemical Vapor Deposition) chamber.
Apparatus embodiments 2 provides a kind of equipment of the carbon granule composite material for the preparation of coated Si, the structural representation of the equipment of the carbon granule composite material for the preparation of coated Si that Fig. 1 provides for apparatus embodiments 2; Described equipment comprises:
I () CVD (Chemical Vapor Deposition) chamber 100, for depositing silicon on carbon particles; Described CVD (Chemical Vapor Deposition) chamber is quartz ampoule; Described quartz ampoule downstream direction comprises the long air inlet section 102 of 5cm, the sample placement section 101 of 10cm length and the air outlet section 103 of 5cm length; Air inlet section 102 internal diameter is identical with air outlet section 103 internal diameter, is 4 ~ 5cm; The internal diameter of described sample placement section 101 is 1.4 ~ 2 times of air inlet section 102 internal diameter;
The sample placement section 101 of described quartz ampoule arranges 4 pieces of baffle plates 104, and described baffle plate 104 is arranged along axis in the shape of a spiral at quartz ampoule inwall, and the hand of spiral is identical with the direction of rotation of CVD (Chemical Vapor Deposition) chamber 100; The spiral starting point of described baffle plate 104 is arranged at 1/3 ~ 1/2 place of CVD (Chemical Vapor Deposition) chamber 100;
Described height of baffle plate is 0.2 ~ 0.5 times of described sample placement section internal diameter;
Preferably, described baffle length is 0.2 ~ 0.5 times of described sample placement section length;
Described baffle plate is wave-shape board;
Fig. 2 is the inwall deployed configuration schematic diagram in axial direction of chemical vapour deposition (CVD) quartz ampoule 100 in apparatus embodiments 2;
(ii) plasma generator 200, for generation of plasma; Described plasma generator comprises radio-frequency power supply 202, and with the inductance-coupled coil 201 of radio-frequency power supply Electricity Federation, described inductance-coupled coil 201 uniform winding is outside CVD (Chemical Vapor Deposition) chamber 101; Described inductance-coupled coil 201 is made up of hollow copper tubing; Described hollow clearance inside is connected with cooling fluid; Described cooling fluid is cooling water;
(iii) gas supply system 300, for supplying silicon source reaction gas to CVD (Chemical Vapor Deposition) chamber; Described gas supply system is 3 ~ 5 air inlet pipe 301 be connected with CVD (Chemical Vapor Deposition) chamber air inlet; Described air inlet pipe can control feed rate; Tracing system 302 is set in described gas supply system, with control temperature at 25 ~ 100 DEG C;
(iv) vacuum system 400, for providing the vacuum of CVD (Chemical Vapor Deposition) chamber;
V () drive unit, horizontally rotates for driving CVD (Chemical Vapor Deposition) chamber; Described drive unit comprises the rotating shaft providing the rotation motor of power and rotated by rotation motor, and described rotating shaft is fixedly connected with CVD (Chemical Vapor Deposition) chamber 100;
(vi) exhaust collection treatment system 600, comprises the cold-trap by cooled with liquid nitrogen, processes for the tail gas collecting generation.
The structural representation of the equipment of the carbon granule composite material for the preparation of coated Si that Fig. 1 provides for apparatus embodiments 2; Fig. 2 is the inwall deployed configuration schematic diagram in axial direction of chemical vapour deposition (CVD) quartz ampoule 100 in apparatus embodiments 2.
Application Example 1
A preparation method for the carbon granule composite material of coated Si, the equipment adopting apparatus embodiments 2 to provide carries out, and comprises the steps:
In the quartz tube sample placement section 101 of CVD (Chemical Vapor Deposition) chamber 100, place the natural spherical plumbago powder of 50g average grain diameter 16 ~ 19 μm of phosphorus content 99.95%, connect equipment by Fig. 1, supply air line is set and accompanies hot temperature 50 C; Pass into 20sccmH
2as carrier gas, be evacuated to 20Pa; After 30min, speed of gyration 5r/min is set, passes into 20sccmSiHCl
3for reaction silicon source, plasma reaction power 200W, at room temperature reacts 2h; Close SiHCl after completion of the reaction
3silicon source is supplied, and continues to use 200W plasma reaction 10min; Take out material, after grinding, screening, obtain nano-silicon/composite cathode material of silicon/carbon/graphite.
Application Example 1 obtains the carbon granule composite material of coated Si, and the silicon layer of described material is non crystalline structure, and silicone content is about 3wt%; Fig. 3 is the scanning electron microscope image that Application Example 1 obtains the carbon granule composite material of coated Si, and silicon nanoparticle uniform deposition is on graphite granule surface as we can see from the figure.
Application Example 2
A preparation method for the carbon granule composite material of coated Si, the equipment adopting apparatus embodiments 2 to provide carries out, and comprises the steps:
In the quartz tube sample placement section 101 of CVD (Chemical Vapor Deposition) chamber 100, place 30g average grain diameter 16 ~ 19 μm, the natural spherical plumbago powder of phosphorus content 99.95%, connects equipment by Fig. 1, arranges supply air line and accompanies hot temperature 50 C, pass into 35sccmH
2as carrier gas, be evacuated to 25Pa, pass into H
2after 30min, speed of gyration 5r/min is set, passes into 20sccmSiHCl
3for reaction silicon source, plasma reaction power 200W, at room temperature reacts 2h, stops the supply of silicon source after completion of the reaction, continues to use 200W plasma reaction 10min; Take out material, after grinding, screening, obtain nano-silicon/composite cathode material of silicon/carbon/graphite.
Application Example 2 obtains the carbon granule composite material of coated Si, and the silicon layer of described material is non crystalline structure, and silicone content is about 10wt%.
Application Example 3
A preparation method for the carbon granule composite material of coated Si, the equipment adopting apparatus embodiments 2 to provide carries out, and comprises the steps:
In the quartz tube sample placement section 101 of CVD (Chemical Vapor Deposition) chamber 100, place 25g average grain diameter 16 ~ 19 μm, the natural spherical plumbago powder of phosphorus content 99.95%, connects equipment by Fig. 1, arranges supply air line and accompanies hot temperature 50 C, pass into 35sccmH
2as carrier gas, be evacuated to 25Pa, pass into H
2after 30min, speed of gyration 5r/min is set, passes into 25sccmSiHCl
3for reaction silicon source, plasma reaction power 200W, at room temperature reacts 4h; Stop the supply of silicon source after completion of the reaction, continue to use 200W plasma reaction 10min; Take out material, after grinding, screening, obtain nano-silicon/composite cathode material of silicon/carbon/graphite.
Application Example 3 obtains the carbon granule composite material of coated Si, and the silicon layer of described material is non crystalline structure, and silicone content is about 25wt%.
Application Example 4
A preparation method for the carbon granule composite material of coated Si, the equipment adopting apparatus embodiments 2 to provide carries out, and comprises the steps:
In the quartz tube sample placement section 101 of CVD (Chemical Vapor Deposition) chamber 100, place 20g average grain diameter 16 ~ 19 μm, the natural spherical plumbago powder of phosphorus content 99.95%, connects equipment by Fig. 1, passes into 20sccmAr as carrier gas, is evacuated to 15Pa; After passing into Ar30min, speed of gyration 10r/min is set, passes into 35sccmSiH
4for reaction silicon source, plasma reaction power 200W, at room temperature reacts 4h; Stop the supply of silicon source after completion of the reaction, continue to use 200W plasma reaction 10min; Take out material, after grinding, screening, obtain nano-silicon/composite cathode material of silicon/carbon/graphite.
Application Example 4 obtains the carbon granule composite material of coated Si, and the silicon layer of described material is non crystalline structure, and silicone content is about 30wt%.
Application Example 5
Be with the difference of Application Example 4, the temperature of CVD (Chemical Vapor Deposition) chamber is adjusted to 700 DEG C, the silicon layer of the carbon granule composite material of the coated Si prepared is crystalline silicon, and silicone content is still 30wt%.
Illustrative examples 1
A preparation method for silicon nanoparticle, the equipment adopting apparatus embodiments 2 to provide carries out, and comprises the steps:
In the quartz tube sample placement section 101 of CVD (Chemical Vapor Deposition) chamber 100, do not place any substrate, connect equipment by Fig. 1, supply air line is set and accompanies hot temperature 50 C, pass into 20sccmAr as carrier gas, be evacuated to 15Pa; After 30min, pass into 10sccmSiHCl
3for reaction silicon source, plasma reaction power 200W is set, at room temperature reacts 2h, deposit one deck nano-silicon at quartzy tube wall; Close SiHCl after completion of the reaction
3silicon source is supplied, and continues to use 200W plasma reaction 10min; Take out material, after grinding, screening, obtain pure silicon nanoparticle material.
Fig. 4 is the X ray diffracting spectrum of illustrative examples 1 gained silicon nanoparticle, be centrally located at the crystal plane of the diffraction maximum corresponding crystalline silicon of difference (111) of 28.4 °, 47.3 °, 56.1 °, (220), (311), but peak intensity is very low, and peak shape broadening clearly; This illustrates that illustrative examples 1 gained silicon nanoparticle is amorphous state.
Fig. 5 is the scanning electron microscope image of illustrative examples 1 gained silicon nanoparticle, and can see silicon grain size uniform, sphericity is high, and average grain diameter is about 40nm.
Illustrative examples 2:
A preparation method for silicon nanoparticle, the equipment adopting apparatus embodiments 2 to provide carries out, and comprises the steps:
In the quartz tube sample placement section 101 of CVD (Chemical Vapor Deposition) chamber 100, do not place any substrate, connect equipment by Fig. 1, supply air line is set and accompanies hot temperature 50 C, pass into 20sccmAr as carrier gas, be evacuated to 15Pa, after 30min, pass into 10sccmSiH
4for reaction silicon source, plasma reaction power 100W is set, at room temperature reacts 2h, deposit one deck nano-silicon at quartzy tube wall; Close the supply of silicon source after completion of the reaction, continue to use 100W plasma reaction 10min; Take out material, after grinding, screening, obtain pure nano-silicon powder body material.
Fig. 6 is the scanning electron microscope image of illustrative examples 2 gained silicon nanoparticle, and can see silicon grain size uniform, sphericity is high, and average grain diameter is about 20nm.
Illustrative examples 3
A preparation method for silicon nanoparticle, the equipment adopting apparatus embodiments 2 to provide carries out, and comprises the steps:
In the quartz tube sample placement section 101 of CVD (Chemical Vapor Deposition) chamber 100, do not place any substrate, connect equipment by Fig. 1, supply air line is set and accompanies hot temperature 50 C; Pass into 20sccmAr as carrier gas, be evacuated to 15Pa, conversion zone is heated to 750 DEG C; After 30min, pass into 10sccmSiHCl
3for reaction silicon source, plasma reaction power 200W is set, at room temperature reacts 2h, deposit one deck nano-silicon at quartzy tube wall; Close SiHCl after completion of the reaction
3silicon source is supplied, and continues to use 200W plasma reaction 10min; Take out material, after grinding, screening, obtain pure nano-silicon powder body material.
Fig. 7 is the X-ray diffractogram of illustrative examples 3 gained silicon nanoparticle, can observe obvious crystalline silicon (111), (220), (311) peak, show have silicon metal to exist in sample.
As can be seen from illustrative examples 1 ~ 3, can obtain crystalline silicon at 750 DEG C, under room temperature condition, reaction can obtain amorphous silicon.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for the carbon granule composite material of coated Si, is characterized in that, described method comprises the steps:
(1) granular graphite is placed in inductance coupling high-CVD (Chemical Vapor Deposition) chamber;
(2) the plasma reaction district of silicon source reaction gas to inductance coupling high-CVD (Chemical Vapor Deposition) chamber is passed into, in vacuum atmosphere, silicon source is decomposed, under inductance coupling high-CVD (Chemical Vapor Deposition) chamber rotating condition, carry out chemical vapour deposition (CVD), obtain the graphite granule of Surface coating silicon;
(3) by the graphite granule of Surface coating silicon through grinding, screening, obtain the carbon granule composite material of Surface coating silicon.
2. the method for claim 1, is characterized in that, the average grain diameter of described granular graphite is 5 ~ 25 μm;
Preferably, described silicon source is selected from SiH
4, Si
2h
6, Si
3h
8, SiCl
4, SiHCl
3, Si
2cl
6, SiH
2cl
2or SiH
3the combination of any a kind or at least 2 kinds in Cl;
Preferably, the carrier gas of described silicon source reaction gas is the combination of any a kind or at least 2 kinds in argon gas, hydrogen or nitrogen;
Preferably, in the reaction gas of described silicon source, the concentration in silicon source is 5 ~ 80v%;
Preferably, the speed that passes into of described silicon source reaction gas is 5 ~ 100sccm;
Preferably, the temperature that passes into of described silicon source reaction gas is 25 ~ 100 DEG C;
Preferably, the power of described inductance coupling high is 50 ~ 350W;
Preferably, the temperature of described chemical vapour deposition (CVD) is 25 ~ 900 DEG C, preferably 25 ~ 60 DEG C or 700 ~ 800 DEG C;
Preferably, the rotating speed of described rotation is 1 ~ 10 rev/min.
3., for the preparation method's of the carbon granule composite material of a coated Si as claimed in claim 1 or 2 equipment, it is characterized in that, described equipment comprises:
I () CVD (Chemical Vapor Deposition) chamber, for depositing silicon on carbon particles;
(ii) plasma generator, for generation of plasma; Described plasma generator comprises radio-frequency power supply, and with the inductance-coupled coil of radio-frequency power supply Electricity Federation, described inductance-coupled coil uniform winding is outside CVD (Chemical Vapor Deposition) chamber;
(iii) gas supply system, for supplying silicon source reaction gas to CVD (Chemical Vapor Deposition) chamber;
(iv) vacuum system, for providing the vacuum of CVD (Chemical Vapor Deposition) chamber;
V () drive unit, horizontally rotates for driving CVD (Chemical Vapor Deposition) chamber.
4. equipment as claimed in claim 3, it is characterized in that, described equipment also comprises (vi) exhaust collection treatment system, processes for the tail gas collecting generation, it comprises the cold-trap by cooled with liquid nitrogen, and described cold-trap is connected with chemical gas-phase deposition system gas outlet;
Preferably, between described cold-trap and chemical gas-phase deposition system gas outlet, metal screen is set;
Preferably, the order number of described metal screen is 200 ~ 500 orders, preferably 200 orders, 325 orders or 500 orders.
5. the equipment as described in claim 3 or 4, is characterized in that, described CVD (Chemical Vapor Deposition) chamber is quartz ampoule, and described quartz ampoule downstream direction comprises air inlet section, sample placement section and air outlet section; Described sample placement section is larger than the caliber of air inlet section and air outlet section;
Preferably, the internal diameter of the quartz ampoule of described air inlet section and air outlet section is 4 ~ 5cm; Preferred described air inlet section is identical with wall thickness with the external diameter of the quartz ampoule of air outlet section;
Preferably, the internal diameter of described sample placement section is 1.4 ~ 2 times of air inlet section internal diameter;
Preferably, the length of described sample placement section is 10 ~ 30cm.
6. equipment as claimed in claim 5, it is characterized in that, the sample placement section of described quartz ampoule arranges at least one piece of baffle plate, and described baffle plate is arranged in the shape of a spiral along axis wall in quartz ampoule, and the hand of spiral is identical with the direction of rotation of CVD (Chemical Vapor Deposition) chamber; The spiral starting point of described baffle plate is arranged at 1/3 ~ 1/2 place of CVD (Chemical Vapor Deposition) chamber;
Preferably, described height of baffle plate is 0.2 ~ 0.5 times of described sample placement section internal diameter;
Preferably, described baffle length is 0.2 ~ 0.5 times of described sample placement section length;
Preferably, described baffle plate is straight plate or wave-shape board, preferred wave-shape board;
Preferably, described baffle plate number is 3 ~ 6 pieces, and every block baffle plate spiral starting point is evenly distributed on the interior cross section of quartz tube sample placement section, and on same circumference.
7. the equipment as described in one of claim 3 ~ 6, is characterized in that, described inductance-coupled coil is made up of hollow copper tubing;
Preferably, described hollow copper tubing inside is connected with cooling fluid;
Preferably, described cooling fluid is cooling water.
8. the equipment as described in one of claim 3 ~ 7, is characterized in that, described gas supply system is at least 1 air inlet pipe be connected with CVD (Chemical Vapor Deposition) chamber air inlet, preferably 3 ~ 5 air inlet pipe;
Preferably, described air inlet pipe can control feed rate;
Preferably, in described gas supply system, tracing system is set, with control temperature at 25 ~ 100 DEG C;
Preferably, described drive unit comprises the rotating shaft providing the rotation motor of power and rotated by rotation motor, and described rotating shaft is fixedly connected with the quartz ampoule of CVD (Chemical Vapor Deposition) chamber.
9. the carbon granule composite material of coated Si for preparing of method as claimed in claim 1 or 2, it is characterized in that, described composite material is the silicon layer of carbon granule external sheath non crystalline structure, or the silicon layer of carbon granule external sheath crystal structure;
Preferably, as the described chemical vapour deposition (CVD) temperature < of claim 1 step (2) 600 DEG C, the composite material of non crystalline structure silicon carbon coated particle is obtained;
Preferably, when described chemical vapour deposition (CVD) temperature >=650 DEG C of claim 1 step (2), the composite material of crystal structure silicon carbon coated particle is obtained;
Preferably, the particle diameter of the carbon granule composite material of described coated Si is 5 ~ 1000nm.
10. a using method for the carbon granule composite material of coated Si as claimed in claim 9, is characterized in that, the carbon granule composite material of described coated Si is used for lithium ion battery negative material;
Preferably, the content of carbon granule composite material in lithium ion battery negative material of described coated Si is 0.1 ~ 100wt%, preferably 0.5 ~ 60wt%, further preferred 1 ~ 30wt%.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058207A (en) * | 2016-08-02 | 2016-10-26 | 中国科学技术大学 | Silicon-carbon composite material, preparation method thereof and negative pole for lithium-ion battery |
| CN106435531A (en) * | 2016-10-12 | 2017-02-22 | 安徽贝意克设备技术有限公司 | Rotational PECVD system |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958842A (en) * | 2006-10-31 | 2007-05-09 | 浙江大学 | Method for preparing bilaminar composite film of aluminum / hydrogenized amorphous silicon carbon alloy |
| US20080261116A1 (en) * | 2007-04-23 | 2008-10-23 | Burton David J | Method of depositing silicon on carbon materials and forming an anode for use in lithium ion batteries |
| CN102651476A (en) * | 2012-05-28 | 2012-08-29 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon carbide composite anode material and preparation method thereof |
| CN104577084A (en) * | 2015-01-20 | 2015-04-29 | 深圳市贝特瑞新能源材料股份有限公司 | Nano silicon composite negative electrode material for lithium ion battery, preparation method and lithium ion battery |
-
2015
- 2015-08-13 CN CN201510494335.8A patent/CN105185970B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958842A (en) * | 2006-10-31 | 2007-05-09 | 浙江大学 | Method for preparing bilaminar composite film of aluminum / hydrogenized amorphous silicon carbon alloy |
| US20080261116A1 (en) * | 2007-04-23 | 2008-10-23 | Burton David J | Method of depositing silicon on carbon materials and forming an anode for use in lithium ion batteries |
| CN102651476A (en) * | 2012-05-28 | 2012-08-29 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon carbide composite anode material and preparation method thereof |
| CN104577084A (en) * | 2015-01-20 | 2015-04-29 | 深圳市贝特瑞新能源材料股份有限公司 | Nano silicon composite negative electrode material for lithium ion battery, preparation method and lithium ion battery |
Non-Patent Citations (3)
| Title |
|---|
| 姜建华: "《无机非金属材料工艺原理》", 31 January 2005, 化学工业出版社 * |
| 樊东黎、潘建生、徐跃明、佟晓辉: "《热处理技术手册》", 31 July 2009, 化学工业出版社 * |
| 邓世均: "《高性能陶瓷涂层》", 31 January 2004, 化学工业出版社 * |
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