CN105185970B - A kind of carbon particle composite material, preparation method and the equipment and purposes of coated Si - Google Patents

A kind of carbon particle composite material, preparation method and the equipment and purposes of coated Si Download PDF

Info

Publication number
CN105185970B
CN105185970B CN201510494335.8A CN201510494335A CN105185970B CN 105185970 B CN105185970 B CN 105185970B CN 201510494335 A CN201510494335 A CN 201510494335A CN 105185970 B CN105185970 B CN 105185970B
Authority
CN
China
Prior art keywords
equipment
silicon
cvd chamber
composite material
carbon particle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510494335.8A
Other languages
Chinese (zh)
Other versions
CN105185970A (en
Inventor
李伟
夏雨
任建国
岳敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Beiteri New Energy Technology Research Institute Co ltd
Original Assignee
Shenzhen BTR New Energy Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen BTR New Energy Materials Co Ltd filed Critical Shenzhen BTR New Energy Materials Co Ltd
Priority to CN201510494335.8A priority Critical patent/CN105185970B/en
Publication of CN105185970A publication Critical patent/CN105185970A/en
Application granted granted Critical
Publication of CN105185970B publication Critical patent/CN105185970B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The present invention relates to carbon particle composite material, preparation method and the equipment and purposes of a kind of coated Si, the present invention prepares nano-silicon using reaction of low temperature plasma decomposition, product can be prepared in chemical vapor deposition under normal temperature condition, obtain the carbon particle of cladding amorphous silicon layer；It is further advanced by the adjusting of reaction gas flow speed, reaction power, can effectively regulate and control silicon nanoparticle size, can freely be controlled within the scope of 5~1000nm；By the way that CVD chamber is designed to rotation mode, nano-silicon and the compound uniformity of substrate can be effectively improved；Further, by the way that the controllable silicon layer of thickness can be obtained to the control of the conditions such as chemical vapor deposition rate, the speed of rotation.

Description

A kind of carbon particle composite material, preparation method and the equipment and purposes of coated Si
Technical field
The present invention relates to the preparation fields more particularly to a kind of coated Si of nano silicon material and lithium ion battery negative material Carbon particle composite material, preparation method and equipment and purposes.
Background technology
Lithium ion battery is the ideal source of portable electronic device, electric vehicle and energy-storage system, exploitation it is higher than energy, Safety is good and low-cost new electrode materials be Study on Li-ion batteries development field core content, novel cathode The research of material is of great significance to the development of lithium ion battery of new generation.
Ripe lithium ion battery negative material is mainly graphite type material at present, and theoretical specific capacity is only 372mAh/ G, development potentiality is limited, cannot be satisfied demand of the following lithium ion battery to high-energy density.Research finds such as Al, Sn, Sb, Si Etc. can be with Li alloyed metal (AM)s and its alloy material, reversible lithium storage capacity be far longer than graphite negative electrodes, such as Si cathode Theoretical capacity be up to 4200mAh/g, but such negative material removal lithium embedded volume expansion shrink it is larger (>300%), high volume Effect causes poor cyclical stability, and making these systems, there are still a certain distance apart from degree of being practical.
In order to improve the cycle performance of silicium cathode, those skilled in the art would generally pass through the nanosizing of silicon, silicon and metal Alloying, the compound of silicon and carbon material improve the Volumetric expansion of silicon materials, the wherein composite wood of nano-silicon and graphite Material has larger application prospect, and the synthesis of nano-silicon and evenly dispersed in graphite matrix are key technologies.
CN101527357B discloses a kind of method that pyrolysis prepares silicon-carbon composite cathode material, using nano-silicon in Core, organic cracking form amorphous carbon coating layer, prepare nano-silicon/amorphous carbon composite negative pole material of nucleocapsid. CN104332621A discloses a kind of method preparing hollow Nano silicon structure, and using metallothermic reduction silica, preparation is received Rice silicon particle, then by non-zinc oxide-silicon dioxide inside acid etch, obtain hollow Nano silicon ball.Both methods does not solve to receive The evenly dispersed problem of rice silicon and graphite base, and preparation process is relatively complicated and bad control.
CN102214817A discloses a kind of carbon/silicon/carbon nano composite structure cathode material and preparation method thereof, passing through It learns gas-phase deposition and deposits nano-silicon on carbon base body, then nanometer is coated in nanometer silicon face by chemical vapor deposition method Carbon；Carbon matrix material is porous carbon, carbon nanotube or graphene.The hole of common porous carbon materials (such as activated carbon) is smaller, It is difficult to effectively carry nano silicon material, and carbon nanotube or graphene itself are easy to reunite, it is also difficult to realize that nano silicon material exists The uniform deposition on its surface.
Therefore, the controllable nano-silicon of particle size uniformity how is simply and effectively prepared, and keeps it uniformly multiple with carbon material It closes, is that there is an urgent need for the technical barriers of solution for field of lithium ion battery.
Invention content
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of carbon particle composite materials of coated Si Preparation method, described method includes following steps：
(1) granular graphite is placed in inductive coupling-CVD chamber；
(2) silicon source reaction gas is passed through to the plasma reaction area of inductive coupling-CVD chamber, in vacuum atmosphere In, silicon source is decomposed, under inductive coupling-CVD chamber rotating condition, carries out chemical vapor deposition, obtains surface packet Cover the graphite particle of silicon；
(3) graphite particle of surface coated Si is ground, screening, obtains the carbon particle composite material of surface coated Si.
Using plasma of the present invention enhances chemical vapor deposition manner, low temperature preparation nanometer silicon composite material；And pass through Swinging tube furnace obtains the carbon particle composite material of coated Si in granular carbon material surface Dynamic deposition silicon.The present invention is logical It crosses and rotates the compound uniformity that compound mode improves nano-silicon and carbon particle substrate.Method provided by the invention is simply easy Row, is easy industrialized production, and the carbon particle composite material for the coated Si being prepared has high power capacity, high first charge discharge efficiency, longevity The features such as life.
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, the silicon source is selected from SiH4、Si2H6、Si3H8、SiCl4、SiHCl3、Si2Cl6、SiH2Cl2Or SiH3In Cl Arbitrary a kind or at least two kinds of of combination.
Preferably, the carrier gas of the silicon source reaction gas is arbitrary a kind or at least two kinds of of the group in argon gas, hydrogen or nitrogen It closes.
Preferably, in the silicon source reaction gas silicon source a concentration of 5~80v%, such as 7v%, 20v%, 32v%, 45v%, 58v%, 63v%, 75v%, 78v% etc..
Preferably, the silicon source reaction gas be passed through speed be 5~100sccm, such as 8sccm, 15sccm, 35sccm, 58sccm, 75sccm, 88sccm, 96sccm etc..
Preferably, the silicon source reaction gas be passed through temperature be 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 the inductive coupling be 50~350W, such as 60W, 80W, 120W, 150W, 180W, 230W, 280W, 310W, 340W etc..
Preferably, the temperature of the chemical vapor deposition be 25~900 DEG C, such as 30 DEG C, 40 DEG C, 100 DEG C, 300 DEG C, It 500 DEG C, 600 DEG C, 800 DEG C etc., preferably 25~60 DEG C or 700~800 DEG C, is obtained when chemical vapor deposition temperature is 25~60 DEG C To the carbon particle composite material of cladding amorphous silicon, cladding crystalline silicon is obtained when chemical vapor deposition temperature is 700~800 DEG C Carbon particle composite material.
Preferably, the rotating speed of the 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 particle composite material of coated Si of the present invention, silicon source concentration in silicon source reaction gas, It is passed through speed and the reaction temperature of CVD chamber, inductive coupling power is related with the speed of chemical vapor deposition, and The rotary speed of CVD chamber, the speed of chemical vapor deposition and time determine that the cladding of carbon particle surface silicon layer is equal Even property.The present invention carries out chemical vapor deposition under the conditions of 25~60 DEG C can obtain amorphous silicon layer.
The second object of the present invention is to provide a kind of carbon particle composite material for the coated Si as described in the first purpose Preparation method equipment, the equipment includes：
(i) CVD chamber, for depositing silicon on carbon particles；
(ii) plasma generator, for generating plasma；The plasma generator includes radio-frequency power supply, and With the inductance-coupled coil of radio-frequency power supply Electricity Federation, the inductance-coupled coil uniform winding is on the outside of CVD chamber；
(iii) gas supply system, for supplying silicon source reaction gas to CVD chamber；
(iv) vacuum system, the vacuum for providing CVD chamber；
(v) driving device, for driving CVD chamber to horizontally rotate.
It is used provided by the present invention for the equipment setting driving device of the preparation method of the carbon particle composite material of coated Si In driving CVD chamber to horizontally rotate, to Dynamic deposition, the carbon particle composite material for the coated Si having good uniformity.
Preferably, the equipment further includes (vi) exhaust collection processing system, is handled for collecting the tail gas generated, It includes the cold-trap cooled down by liquid nitrogen, and the cold-trap is connect with chemical gas-phase deposition system gas outlet.Exhaust collection processing system System can effectively avoid the pollution to environment and the corrosion to vacuum equipment.
Preferably, metal screen is set between the cold-trap and chemical gas-phase deposition system gas outlet；
Preferably, the mesh number of the metal screen is 200~500 mesh, preferably 200 mesh, 325 mesh or 500 mesh.
The metal screen can effectively stop carbon particle, avoid its influence to vacuum equipment.
The CVD chamber is quartz ampoule, and the quartz ampoule downstream direction includes air inlet section, sample placement section And air outlet section；The sample placement section is bigger than the caliber of air inlet section and air outlet section.
Preferably, the internal diameter of the quartz ampoule of the air inlet section and air outlet section is 4~5cm, such as 4.3cm, 4.6cm, 4.8cm Deng；It is preferred that the air inlet section is identical with the internal diameter of the quartz ampoule of air outlet section.
Preferably, the internal diameter of the sample placement section is 1.4~2 times of air inlet section internal diameter, for example, 1.5 times, 1.6 times, 1.7 Again, 1.8 times, 1.9 times etc..
Preferably, the length of the sample placement section is 10~30cm.
An at least block baffle is arranged in the sample placement section of the quartz ampoule, and the baffle is in spiral shell along axis in quartzy inside pipe wall Shape setting is revolved, the hand of spiral is identical as the direction of rotation of CVD chamber；The spiral starting point of the baffle is set to chemistry At the 1/3~1/2 of vapor deposition chamber；
Preferably, the height of baffle plate is 0.2~0.5 times of the sample placement section internal diameter, for example, 0.3 times, 0.4 times, 0.5 times etc..
Preferably, the baffle length is that the sample places 0.2~0.5 times of segment length, for example, 0.3 times, 0.4 times, 0.5 times etc..
Preferably, the baffle is straight panel or wave-shape board, preferably wave-shape board；
Preferably, the baffle number is 3~6 pieces, and quartz tube sample placement is evenly distributed on per block baffle spiral starting point In the inner section of section, and on same circumference.
The caliber of quartz tube sample placement section is set as big compared with the caliber of air inlet section and air outlet section by the present invention, can be effective Ground extends residence time of the granular graphite in CVD chamber, prevents from flowing out with air-flow in granular graphite.Into one Step ground, the present invention by the specific setting of structure and arrangement to baffle, can significantly more efficient extension granular graphite changing The residence time in vapor deposition chamber is learned, the speed of reaction and the deposition uniformity of silicon layer are improved.
Inductance-coupled coil of the present invention is made of hollow copper tubing.
Preferably, it is connected with coolant liquid inside the hollow copper tubing.
Preferably, the coolant liquid is cooling water.
Gas supply system of the present invention is at least 1 air inlet pipe being connect with CVD chamber air inlet, excellent Select 3~5 air inlet pipe.
Preferably, the air inlet pipe can control feed rate.
Preferably, tracing system is set in the gas supply system, to control temperature at 25~100 DEG C.
Driving device of the present invention includes the rotary shaft for providing the rotation motor of power and being rotated by rotation motor, described Rotary shaft is fixedly connected with the quartz ampoule of CVD chamber.
The third object of the present invention is to provide a kind of carbon particle for the coated Si being prepared such as first purpose the method Composite material, the composite material are the silicon layer or carbon particle external sheath crystal structure of carbon particle external sheath non crystalline structure Silicon layer.
Preferably, as 600 DEG C of claim 1 step (2) the chemical vapor deposition temperature <, non crystalline structure silicon is obtained Coat the composite material of carbon particle；
Preferably, when claim 1 step (2) chemical vapor deposition temperature >=650 DEG C, crystal structure silicon is obtained Coat the composite material of carbon particle；
Preferably, the grain size of the carbon particle composite material of the coated Si be 5~1000nm, such as 8nm, 18nm, 50nm, 180nm, 240nm, 380nm, 700nm, 850nm, 980nm etc..
The four of the object of the invention are to provide a kind of user of the carbon particle composite material of the coated Si as described in the third purpose The carbon particle composite material of the coated Si is used for lithium ion battery negative material by method.
Preferably, content of the carbon particle composite material of the coated Si in lithium ion battery negative material be 0.1~ 100wt%, preferably 0.5~60wt%, further preferred 1~30wt%.
Compared with prior art, the present invention has the advantages that：
(1) present invention prepares nano-silicon using reaction of low temperature plasma decomposition, can be in room temperature (25~60 DEG C) condition Lower chemical vapor deposition prepares product, obtains the carbon particle of cladding amorphous silicon layer；It is further advanced by reaction gas flow speed, reaction work( The adjusting of rate can regulate and control silicon nanoparticle size, can freely be controlled within the scope of 5~1000nm；
(2) present invention can control the crystalline state of silicon in composite material by the change of CVD chamber temperature；? Low temperature (<600 DEG C) under the conditions of can obtain amorphous nano silicon, crystalline state nanometer is can get under the conditions of high temperature (>=650 DEG C) Silicon；
(3) by the way that CVD chamber is designed to rotation mode, it is compound with substrate nano-silicon can effectively to be improved Uniformity；Further, can to obtain thickness by the control to conditions such as chemical vapor deposition rate, the speeds of rotation controllable Silicon layer.
It is (4) of the invention by the way that the caliber of quartz tube sample placement section is set as big compared with the caliber of air inlet section and air outlet section, Residence time of the granular graphite in CVD chamber can effectively be extended, prevented in granular graphite with air-flow stream Go out；Further, the present invention is by the specific setting of structure and arrangement to baffle, such as will keep off baffle plate setting at wavy Plate is set as the arrangement of helical form, and specific height of baffle plate etc. and baffle circumferentially, to obtaining longer graininess Residence time of the graphite in CVD chamber, the uniformity for further increasing reaction speed and silicon layer have positive work With.
Description of the drawings
Fig. 1 is the structural representation of the equipment for the carbon particle composite material for being used to prepare coated Si that apparatus embodiments 2 provide Figure；100 CVD chambers；101 quartz tube sample placement sections；102 quartz ampoule air inlet sections；103 quartz ampoule air outlet sections；200 Plasma generator；201 inductance-coupled coils；202 radio-frequency power supplies；300 gas supply systems；301 air inlet pipe；302 heat tracings System；400 vacuum systems；600 exhaust collection processing systems, 601 metal filter screens；
Fig. 2 is the deployed configuration signal of the inner wall of chemical vapor deposition quartz ampoule 100 in apparatus embodiments 2 in axial direction Figure；104 baffles；
Fig. 3 is the scanning electron microscope image for the carbon particle composite material that Application Example 1 obtains coated Si；
Fig. 4 is the X ray diffracting spectrum for illustrating 1 gained silicon nanoparticle of example；
Fig. 5 is the scanning electron microscope image for illustrating 1 gained silicon nanoparticle of example；
Fig. 6 is the scanning electron microscope image for illustrating 2 gained silicon nanoparticle of example；
Fig. 7 is the X-ray diffractogram for illustrating 3 gained silicon nanoparticle of example.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Apparatus embodiments 1 provide a kind of equipment for the carbon particle composite material being used to prepare coated Si, the equipment packet It includes：
(i) CVD chamber 100, for depositing silicon on carbon particles；
(ii) plasma generator 200, for generating plasma；The plasma generator includes radio-frequency power supply 202, and the inductance-coupled coil 201 with radio-frequency power supply Electricity Federation, the inductance-coupled coil uniform winding is in chemical vapor deposition Outside；
(iii) gas supply system 300, for supplying silicon source reaction gas to CVD chamber；
(iv) vacuum system 400, the vacuum for providing CVD chamber；
(v) driving device, for driving CVD chamber to horizontally rotate.
Apparatus embodiments 2 provide a kind of equipment for the carbon particle composite material being used to prepare coated Si, and Fig. 1 is that equipment is real The structural schematic diagram of the equipment of the carbon particle composite material for being used to prepare coated Si of the offer of example 2 is provided；The equipment includes：
(i) CVD chamber 100, for depositing silicon on carbon particles；The CVD chamber is quartz ampoule； The quartz ampoule downstream direction includes the air inlet section 102, the sample placement section 101 of 10cm long and the air outlet section of 5cm long of 5cm long 103；102 internal diameter of air inlet section is identical as 103 internal diameter of air outlet section, is 4~5cm；The internal diameter of the sample placement section 101 is air inlet 1.4~2 times of 102 internal diameters of section；
4 block baffles 104 are arranged in the sample placement section 101 of the quartz ampoule, and the baffle 104 is in quartzy inside pipe wall along axis It is arranged in the shape of a spiral, the hand of spiral is identical as the direction of rotation of CVD chamber 100；The spiral starting point of the baffle 104 It is set at the 1/3~1/2 of CVD chamber 100；
The height of baffle plate is 0.2~0.5 times of the sample placement section internal diameter；
Preferably, the baffle length is that the sample places 0.2~0.5 times of segment length；
The baffle is wave-shape board；
Fig. 2 is the deployed configuration signal of the inner wall of chemical vapor deposition quartz ampoule 100 in apparatus embodiments 2 in axial direction Figure；
(ii) plasma generator 200, for generating plasma；The plasma generator includes radio-frequency power supply 202, and the inductance-coupled coil 201 with radio-frequency power supply Electricity Federation, 201 uniform winding of the inductance-coupled coil is in chemical vapor deposition 101 outside of product room；The inductance-coupled coil 201 is made of hollow copper tubing；It is connected with coolant liquid inside the hollow clearance；It is described Coolant liquid is cooling water；
(iii) gas supply system 300, for supplying silicon source reaction gas to CVD chamber；The gas supply System is 3~5 air inlet pipe 301 being connect with CVD chamber air inlet；The air inlet pipe can control feed rate； Tracing system 302 is set in the gas supply system, to control temperature at 25~100 DEG C；
(iv) vacuum system 400, the vacuum for providing CVD chamber；
(v) driving device, for driving CVD chamber to horizontally rotate；The driving device includes providing power Rotation motor and the rotary shaft rotated by rotation motor, the rotary shaft are fixedly connected with CVD chamber 100；
(vi) exhaust collection processing system 600 includes the cold-trap cooled down by liquid nitrogen, is carried out for collecting the tail gas generated Processing.
Fig. 1 is the structural representation of the equipment for the carbon particle composite material for being used to prepare coated Si that apparatus embodiments 2 provide Figure；Fig. 2 is the deployed configuration schematic diagram of the inner wall of chemical vapor deposition quartz ampoule 100 in apparatus embodiments 2 in axial direction.
Application Example 1
A kind of preparation method of the carbon particle composite material of coated Si is carried out, packet using the equipment that apparatus embodiments 2 provide Include following steps：
It is carbon containing that 16~19 μm of 50g average grain diameters are placed in the quartz tube sample placement section 101 of CVD chamber 100 The natural spherical plumbago powder of amount 99.95% connects equipment by Fig. 1, supply air line heat tracing temperature 50 C is arranged；It is passed through 20sccm H2As carrier gas, it is evacuated to 20Pa；After 30min, rotational speed 5r/min is set, 20sccm SiHCl are passed through3To react silicon Source, plasma reaction power 200W, reacts 2h at room temperature；SiHCl is closed after completion of the reaction3Silicon source is supplied, and is continuing with 200W plasma reactions 10min；Material is taken out, nano-silicon/composite cathode material of silicon/carbon/graphite is obtained after ground, screening.
Application Example 1 obtains the carbon particle composite material of coated Si, and the silicon layer of the material is non crystalline structure, silicone content About 3wt%；Fig. 3 is the scanning electron microscope image for the carbon particle composite material that Application Example 1 obtains coated Si, can from figure To silicon nanoparticle uniform deposition on graphite particle surface.
Application Example 2
A kind of preparation method of the carbon particle composite material of coated Si is carried out, packet using the equipment that apparatus embodiments 2 provide Include following steps：
16~19 μm of 30g average grain diameters are placed in the quartz tube sample placement section 101 of CVD chamber 100, are contained The natural spherical plumbago powder of carbon amounts 99.95% connects equipment by Fig. 1, supply air line heat tracing temperature 50 C is arranged, is passed through 35sccm H2As carrier gas, it is evacuated to 25Pa, is passed through H2After 30min, rotational speed 5r/min is set, 20sccm is passed through SiHCl3To react silicon source, plasma reaction power 200W reacts 2h at room temperature, stops silicon source supply after completion of the reaction, It is continuing with 200W plasma reactions 10min；Material is taken out, nano-silicon/graphite composite negative pole material is obtained after ground, screening Material.
Application Example 2 obtains the carbon particle composite material of coated Si, and the silicon layer of the material is non crystalline structure, silicone content About 10wt%.
Application Example 3
A kind of preparation method of the carbon particle composite material of coated Si is carried out, packet using the equipment that apparatus embodiments 2 provide Include following steps：
16~19 μm of 25g average grain diameters are placed in the quartz tube sample placement section 101 of CVD chamber 100, are contained The natural spherical plumbago powder of carbon amounts 99.95% connects equipment by Fig. 1, supply air line heat tracing temperature 50 C is arranged, is passed through 35sccm H2As carrier gas, it is evacuated to 25Pa, is passed through H2After 30min, rotational speed 5r/min is set, 25sccm is passed through SiHCl3To react silicon source, plasma reaction power 200W reacts 4h at room temperature；Stop silicon source supply after completion of the reaction, It is continuing with 200W plasma reactions 10min；Material is taken out, nano-silicon/graphite composite negative pole material is obtained after ground, screening Material.
Application Example 3 obtains the carbon particle composite material of coated Si, and the silicon layer of the material is non crystalline structure, silicone content About 25wt%.
Application Example 4
A kind of preparation method of the carbon particle composite material of coated Si is carried out, packet using the equipment that apparatus embodiments 2 provide Include following steps：
16~19 μm of 20g average grain diameters are placed in the quartz tube sample placement section 101 of CVD chamber 100, are contained The natural spherical plumbago powder of carbon amounts 99.95%, equipment is connected by Fig. 1, is passed through 20sccm Ar as carrier gas, is evacuated to 15Pa；After being passed through Ar 30min, rotational speed 10r/min is set, 35sccm SiH are passed through4To react silicon source, plasma is anti- Power 200W is answered, reacts 4h at room temperature；Stop silicon source supply after completion of the reaction, is continuing with 200W plasma reactions 10min；Material is taken out, nano-silicon/composite cathode material of silicon/carbon/graphite is obtained after ground, screening.
Application Example 4 obtains the carbon particle composite material of coated Si, and the silicon layer of the material is non crystalline structure, silicone content About 30wt%.
Application Example 5
Difference lies in be adjusted to 700 DEG C by the temperature of CVD chamber, be prepared with Application Example 4 The silicon layer of the carbon particle composite material of coated Si is crystalline silicon, and silicone content is still 30wt%.
Illustrate example 1
A kind of preparation method of silicon nanoparticle is carried out using the equipment that apparatus embodiments 2 provide, is included the following steps：
Any substrate is not placed in the quartz tube sample placement section 101 of CVD chamber 100, is connected by Fig. 1 Equipment is arranged supply air line heat tracing temperature 50 C, is passed through 20sccm Ar as carrier gas, is evacuated to 15Pa；After 30min, lead to Enter 10sccm SiHCl3To react silicon source, plasma reaction power 200W is set, 2h is reacted at room temperature, in quartzy tube wall Deposit one layer of nano-silicon；SiHCl is closed after completion of the reaction3Silicon source is supplied, and 200W plasma reactions 10min is continuing with；It takes Go out material, pure silicon nanoparticle material is obtained after ground, screening.
Fig. 4 is the X ray diffracting spectrum for illustrating 1 gained silicon nanoparticle of example, and center is located at 28.4 °, 47.3 °, 56.1 ° Diffraction maximum correspond to respectively crystalline silicon (111), (220), (311) crystal plane, but peak intensity is very low, and peak shape broadening is non- Chang Mingxian；This illustrates that 1 gained silicon nanoparticle of example is amorphous state.
Fig. 5 is the scanning electron microscope image for illustrating 1 gained silicon nanoparticle of example, it can be seen that silicon particle size uniform is spherical Degree is high, average grain diameter about 40nm.
Illustrate example 2：
A kind of preparation method of silicon nanoparticle is carried out using the equipment that apparatus embodiments 2 provide, is included the following steps：
Any substrate is not placed in the quartz tube sample placement section 101 of CVD chamber 100, is connected by Fig. 1 Equipment is arranged supply air line heat tracing temperature 50 C, is passed through 20sccm Ar as carrier gas, is evacuated to 15Pa, after 30min, leads to Enter 10sccm SiH4To react silicon source, plasma reaction power 100W is set, reacts 2h at room temperature, is sunk in quartzy tube wall One layer of nano-silicon of product；Silicon source supply is closed after completion of the reaction, is continuing with 100W plasma reactions 10min；Take out material, warp Pure nano-silicon powder body material is obtained after grinding, screening.
Fig. 6 is the scanning electron microscope image for illustrating 2 gained silicon nanoparticle of example, it can be seen that silicon particle size uniform is spherical Degree is high, average grain diameter about 20nm.
Illustrate example 3
A kind of preparation method of silicon nanoparticle is carried out using the equipment that apparatus embodiments 2 provide, is included the following steps：
Any substrate is not placed in the quartz tube sample placement section 101 of CVD chamber 100, is connected by Fig. 1 Supply air line heat tracing temperature 50 C is arranged in equipment；20sccm Ar are passed through as carrier gas, are evacuated to 15Pa, conversion zone heating It is warming up to 750 DEG C；After 30min, it is passed through 10sccm SiHCl3For reaction silicon source, plasma reaction power 200W is set, 2h is reacted at room temperature, and one layer of nano-silicon is deposited in quartzy tube wall；SiHCl is closed after completion of the reaction3Silicon source is supplied, and is continuing with 200W plasma reactions 10min；Material is taken out, pure nano-silicon powder body material is obtained after ground, screening.
Fig. 7 is the X-ray diffractogram for illustrating 3 gained silicon nanoparticle of example, it may be observed that apparent crystalline silicon (111), (220), (311) peak shows in sample with the presence of silicon metal.
By illustrating that crystalline silicon can be obtained it can be seen from example 1~3 at 750 DEG C, reaction under room temperature can obtain amorphous Type silicon.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's Within protection domain and the open scope.

Claims (38)

1. a kind of equipment for the carbon particle composite material preparing coated Si, which is characterized in that the equipment includes：
(i) CVD chamber, for depositing silicon on carbon particles；
(ii) plasma generator, for generating plasma；The plasma generator includes radio-frequency power supply, and with penetrate The inductance-coupled coil of frequency power Electricity Federation, the inductance-coupled coil uniform winding is on the outside of CVD chamber；
(iii) gas supply system, for supplying silicon source reaction gas to CVD chamber；
(iv) vacuum system, the vacuum for providing CVD chamber；
(v) driving device, for driving CVD chamber to horizontally rotate；
Wherein, the CVD chamber is quartz ampoule, and the quartz ampoule downstream direction includes air inlet section, sample placement section And air outlet section；The sample placement section is bigger than the caliber of air inlet section and air outlet section；
The sample placement section of the quartz ampoule is arranged an at least block baffle, the baffle in quartz ampoule along axis wall in the shape of a spiral Setting, the hand of spiral are identical as the direction of rotation of CVD chamber；The spiral starting point of the baffle is set to chemical gaseous phase At the 1/3~1/2 of settling chamber.
2. equipment as described in claim 1, which is characterized in that the equipment further includes (vi) exhaust collection processing system, is used It is handled in collecting the tail gas generated comprising the cold-trap cooled down by liquid nitrogen, the cold-trap and chemical gas-phase deposition system Gas outlet connects.
3. equipment as claimed in claim 2, which is characterized in that set between the cold-trap and chemical gas-phase deposition system gas outlet Set metal screen.
4. equipment as claimed in claim 3, which is characterized in that the mesh number of the metal screen is 200~500 mesh.
5. equipment as claimed in claim 4, which is characterized in that the mesh number of the metal screen is 200 mesh, 325 mesh or 500 Mesh.
6. equipment as described in claim 1, which is characterized in that the internal diameter of the quartz ampoule of the air inlet section and air outlet section be 4~ 5cm。
7. equipment as described in claim 1, which is characterized in that the outer diameter and wall thickness of the quartz ampoule of the air inlet section and air outlet section It is identical.
8. equipment as described in claim 1, which is characterized in that the internal diameter of the sample placement section is the 1.4 of air inlet section internal diameter ~2 times.
9. equipment as described in claim 1, which is characterized in that the length of the sample placement section is 10~30cm.
10. equipment as described in claim 1, which is characterized in that the height of baffle plate is the 0.2 of the sample placement section internal diameter ~0.5 times.
11. equipment as described in claim 1, which is characterized in that the baffle length is that the sample places the 0.2 of segment length ~0.5 times.
12. equipment as described in claim 1, which is characterized in that the baffle is straight panel or wave-shape board.
13. equipment as claimed in claim 12, which is characterized in that the baffle is wave-shape board.
14. equipment as described in claim 1, which is characterized in that the baffle number is 3~6 pieces, per block baffle spiral starting point It is evenly distributed in the inner section of quartz tube sample placement section, and on same circumference.
15. equipment as described in claim 1, which is characterized in that the inductance-coupled coil is made of hollow copper tubing.
16. equipment as claimed in claim 15, which is characterized in that be connected with coolant liquid inside the hollow copper tubing.
17. equipment as claimed in claim 16, which is characterized in that the coolant liquid is cooling water.
18. equipment as described in claim 1, which is characterized in that the gas supply system is at least 1 and chemical vapor deposition The air inlet pipe of product room air inlet connection.
19. equipment as claimed in claim 18, which is characterized in that the gas supply system is 3~5 and chemical vapor deposition The air inlet pipe of product room air inlet connection.
20. equipment as claimed in claim 18, which is characterized in that the air inlet pipe can control feed rate.
21. equipment as described in claim 1, which is characterized in that tracing system is arranged in the gas supply system, with control Temperature is at 25~100 DEG C.
22. equipment as described in claim 1, which is characterized in that the driving device include provide power rotation motor and The rotary shaft rotated by rotation motor, the rotary shaft are fixedly connected with the quartz ampoule of CVD chamber.
23. a kind of method for the carbon particle composite material preparing coated Si using claim 1-22 any one of them equipment, It is characterized in that, described method includes following steps：
(1) granular graphite is placed in inductive coupling-CVD chamber；
(2) it is passed through silicon source reaction gas to the plasma reaction area of inductive coupling-CVD chamber, in vacuum atmosphere, Silicon source is decomposed, under inductive coupling-CVD chamber rotating condition, carries out chemical vapor deposition, obtains surface cladding The graphite particle of silicon；
(3) graphite particle of surface coated Si is ground, screening, obtains the carbon particle composite material of surface coated Si；
Wherein, the rotating speed of the rotation is 1~10 rev/min；
Inductive coupling-CVD chamber shape on the outside of CVD chamber by inductance-coupled coil uniform winding At the CVD chamber is quartz ampoule, and the quartz ampoule downstream direction includes air inlet section, sample placement section and outlet Section；The sample placement section is bigger than the caliber of air inlet section and air outlet section；
The sample placement section of the quartz ampoule is arranged an at least block baffle, the baffle in quartz ampoule along axis wall in the shape of a spiral Setting, the hand of spiral are identical as the direction of rotation of CVD chamber；The spiral starting point of the baffle is set to chemical gaseous phase At the 1/3~1/2 of settling chamber.
24. method as claimed in claim 23, which is characterized in that the average grain diameter of the granular graphite is 5~25 μm.
25. method as claimed in claim 23, which is characterized in that the silicon source is selected from SiH4、Si2H6、Si3H8、SiCl4、 SiHCl3、Si2Cl6、SiH2Cl2Or SiH3Arbitrary a kind or at least two kinds of of combination in Cl.
26. method as claimed in claim 23, which is characterized in that the carrier gas of the silicon source reaction gas is argon gas, hydrogen or nitrogen Arbitrary a kind or at least two kinds of of combination in gas.
27. method as claimed in claim 23, which is characterized in that a concentration of the 5 of silicon source in the silicon source reaction gas~ 80v%.
28. method as claimed in claim 23, which is characterized in that the silicon source reaction gas be passed through speed be 5~ 100sccm。
29. method as claimed in claim 23, which is characterized in that the temperature that is passed through of the silicon source reaction gas is 25~100 DEG C.
30. method as claimed in claim 23, which is characterized in that the power of the inductive coupling is 50~350W.
31. according to the method for claim 23, which is characterized in that the temperature of the chemical vapor deposition is 25~900 DEG C.
32. method as claimed in claim 31, which is characterized in that the temperature of the chemical vapor deposition be 25~60 DEG C or 700~800 DEG C.
33. a kind of carbon particle composite material for the coated Si that method as claimed in claim 23 is prepared, which is characterized in that institute State the silicon layer that composite material is carbon particle external sheath non crystalline structure.
34. the carbon particle composite material of coated Si as claimed in claim 33, which is characterized in that the carbon particle of the coated Si The grain size of composite material is 5~1000nm.
35. a kind of application method of the carbon particle composite material of the coated Si as described in claim 33 or 34, which is characterized in that will The carbon particle composite material of the coated Si is used for lithium ion battery negative material.
36. application method as claimed in claim 35, which is characterized in that the carbon particle composite material of the coated Si lithium from Content in sub- cell negative electrode material is 0.1~100wt%.
37. application method as claimed in claim 36, which is characterized in that the carbon particle composite material of the coated Si lithium from Content in sub- cell negative electrode material is 0.5~60wt%.
38. application method as claimed in claim 37, which is characterized in that the carbon particle composite material of the coated Si lithium from Content in sub- cell negative electrode material is 1~30wt%.
CN201510494335.8A 2015-08-13 2015-08-13 A kind of carbon particle composite material, preparation method and the equipment and purposes of coated Si Active CN105185970B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510494335.8A CN105185970B (en) 2015-08-13 2015-08-13 A kind of carbon particle composite material, preparation method and the equipment and purposes of coated Si

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510494335.8A CN105185970B (en) 2015-08-13 2015-08-13 A kind of carbon particle composite material, preparation method and the equipment and purposes of coated Si

Publications (2)

Publication Number Publication Date
CN105185970A CN105185970A (en) 2015-12-23
CN105185970B true CN105185970B (en) 2018-11-02

Family

ID=54907925

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510494335.8A Active CN105185970B (en) 2015-08-13 2015-08-13 A kind of carbon particle composite material, preparation method and the equipment and purposes of coated Si

Country Status (1)

Country Link
CN (1) CN105185970B (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
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
CN106435531B (en) * 2016-10-12 2018-09-18 安徽贝意克设备技术有限公司 A kind of rotation PECVD system
CN106498370B (en) * 2016-12-30 2018-11-16 东莞市天域半导体科技有限公司 A kind of vacuum chamber high temperature CVD heating coil structure
CN108172779A (en) * 2017-12-07 2018-06-15 山东玉皇新能源科技有限公司 SiCl4The method that in-situ deposition prepares the Si-C composite material with micro-nano structure
CN108565408A (en) * 2018-01-10 2018-09-21 电子科技大学 A kind of lithium ion battery negative material and preparation method thereof
CN110034281B (en) * 2018-04-12 2021-06-15 南方科技大学 Phosphorus/carbon composite material, preparation method thereof, lithium ion battery and sodium ion battery
CN109850876A (en) * 2019-02-18 2019-06-07 合肥百思新材料研究院有限公司 A kind of continuous Automatic Control graphene powder baggage systems
CN110592559B (en) * 2019-09-17 2021-08-27 淮北摩兰科技有限公司 Display screen line protection device and method
CN112040743A (en) * 2020-09-09 2020-12-04 广东思泉新材料股份有限公司 Heat conducting fin with coating layer structure
JP2024503167A (en) * 2021-04-16 2024-01-25 ワッカー ケミー アクチエンゲゼルシャフト silicon carbon composite particles
JP2024521849A (en) * 2021-05-28 2024-06-04 アンワイヤー Method for producing silicon-carbon composite material
CN113321215A (en) * 2021-07-06 2021-08-31 浙江中宁硅业有限公司 Carbon-silicon composite particle and preparation method and preparation device thereof
CN113881090B (en) * 2021-10-13 2022-12-27 安徽晟华光学科技有限公司 Diffusion film and preparation method thereof
WO2023117047A1 (en) * 2021-12-20 2023-06-29 Wacker Chemie Ag Process for producing silicon-containing materials in a stirred-tank reactor
WO2023245652A1 (en) * 2022-06-24 2023-12-28 上海杉杉科技有限公司 Spherical silicon-based lithium storage material and preparation method therefor
EP4386899A1 (en) * 2022-11-02 2024-06-19 Contemporary Amperex Technology Co., Limited Negative electrode active material and preparation method therefor, secondary battery comprising same, and electric device

Citations (3)

* Cited by examiner, † Cited by third party
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
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8828481B2 (en) * 2007-04-23 2014-09-09 Applied Sciences, Inc. Method of depositing silicon on carbon materials and forming an anode for use in lithium ion batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
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
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

Also Published As

Publication number Publication date
CN105185970A (en) 2015-12-23

Similar Documents

Publication Publication Date Title
CN105185970B (en) A kind of carbon particle composite material, preparation method and the equipment and purposes of coated Si
US11851332B2 (en) Silicon-carbon composite material and preparation method thereof
Xi et al. PSi@ SiOx/Nano-Ag composite derived from silicon cutting waste as high-performance anode material for Li-ion batteries
JP2023522139A (en) Three-dimensional porous silicon-carbon composite material, its preparation method and its application
CN104347857B (en) Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery
CN102394287A (en) Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof
TWI771447B (en) Silicon-carbon composite powder
CN102208634A (en) Porous silicon/carbon composite material and preparation method thereof
CN104103821B (en) The preparation method of silicon-carbon cathode material
JP2016134382A (en) Nano silicon composite negative electrode material for lithium ion battery, production method and lithium ion battery
CN110165187A (en) A kind of lithium ion battery silicon-carbon second particle material and preparation method thereof
CN112234174A (en) Lithium ion battery cathode material and preparation method thereof
CN102496701A (en) Silicon-carbon alloy cathode material used in lithium ion battery, and preparation method thereof
CN112952054B (en) Silicon-based anode material, preparation method thereof, anode and lithium ion battery
CN110611092B (en) Preparation method of nano silicon dioxide/porous carbon lithium ion battery cathode material
CN108232141A (en) A kind of silicon-carbon composite cathode material of lithium ion battery of high-pressure solid and preparation method thereof
CN108417800B (en) Graphene-coated graphite/metal composite powder negative electrode material and preparation method thereof
CN109286014A (en) A kind of Si-C composite material and its preparation method and application that surface is modified
WO2024130982A1 (en) High-initial-efficiency negative electrode material for lithium-ion secondary battery and preparation method therefor
CN205893385U (en) Chemical vapor deposition device
CN115863600A (en) Silicon-carbon negative electrode material and preparation method and application thereof
CN115954443A (en) Preparation method of carbon-coated silicon-copper alloy negative electrode material of lithium ion battery
CN108598377B (en) Preparation method of sulfur-silicon carbide doped carbon nanotube material
CN113066985A (en) Composite negative electrode material, preparation method thereof and lithium ion battery
CN117199328A (en) Silicon-carbon negative electrode material with high silicon content and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP01 Change in the name or title of a patent holder

Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee after: Beitrei New Materials Group Co.,Ltd.

Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee before: Shenzhen BTR New Energy Materials Inc.

CP01 Change in the name or title of a patent holder
TR01 Transfer of patent right

Effective date of registration: 20230518

Address after: A2001, Building 1, Beiteri Science and Technology Park, No. 26 Baolan Road, Laokeng Community, Longtian Street, Pingshan District, Shenzhen City, Guangdong Province, 518118

Patentee after: Shenzhen beiteri New Energy Technology Research Institute Co.,Ltd.

Address before: 518106 Guangdong Shenzhen Guangming New District Gongming office, saitan community high tech Industrial Park eighth

Patentee before: Beitrei New Materials Group Co.,Ltd.

TR01 Transfer of patent right