CN103456926A - Preparation methods of silicon-graphene composite material and lithium ion battery - Google Patents
Preparation methods of silicon-graphene composite material and lithium ion battery Download PDFInfo
- Publication number
- CN103456926A CN103456926A CN2012101765853A CN201210176585A CN103456926A CN 103456926 A CN103456926 A CN 103456926A CN 2012101765853 A CN2012101765853 A CN 2012101765853A CN 201210176585 A CN201210176585 A CN 201210176585A CN 103456926 A CN103456926 A CN 103456926A
- Authority
- CN
- China
- Prior art keywords
- silicon
- composite material
- graphene composite
- preparation
- negative
- 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.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of a silicon-graphene composite material. The preparation method comprises the following steps of putting a substrate into a reaction chamber of a chemical vapor deposition device, heating the substrate to a temperature of 500-1300 DEG C in a protective atmosphere, feeding a gaseous carbon source and a gaseous silicon source into the reaction chamber for a reaction lasting for 1-300min, and carrying out cooling to obtain the silicon-graphene composite material. The preparation method of the silicon-graphene composite material has the simple processes. The invention also provides a preparation method of a lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of silicon-graphene composite material and the preparation method of lithium ion battery.
Background technology
Graphene is as a kind of new carbon, since within 2004, being found, due to its two-dimentional monolayer structure and excellent physical property, as high theoretical specific area, excellent mechanical strength, good pliability and high conductivity etc., two are widely used in lithium ion battery.By silicon materials and Graphene carry out compound can effectively reduce silicon materials expand and contraction process in to the destruction of electrode material, thereby the cycle performance of raising device.
When preparing at present silicon-Graphene and meeting material, first, by the standby graphite oxide of graphite-made, by graphite oxide, prepare graphene oxide, redox graphene prepares Graphene, finally prepared by silicon materials and Graphene blend again.The preparation method of this silicon-graphene composite material is comparatively loaded down with trivial details.
Summary of the invention
Based on this, be necessary to provide the preparation method of silicon-graphene composite material that a kind of technique is comparatively simple and the preparation method of lithium ion battery.
A kind of preparation method of silicon-graphene composite material, comprise the steps:
Substrate is positioned over to the reative cell of chemical vapor depsotition equipment, under the protective gas atmosphere, heating described substrate, to make described substrate temperature be 500 ℃ ~ 1300 ℃; And
Pass into gaseous carbon source and gaseous state silicon source in described reative cell, the cooling silicon-graphene composite material that obtains after reaction 1min ~ 300min.
In embodiment, described protective gas is nitrogen or argon gas therein.
In embodiment, described gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene therein.
In embodiment, described gaseous state silicon source is selected from least one in tetramethylsilane and silicon tetrahydride therein.
In embodiment, the mol ratio in described gaseous carbon source and described gaseous state silicon source is 0.5:1 ~ 6:1 therein.
In embodiment, the preparation method of described silicon-graphene composite material also comprises step therein: described silicon-graphene composite material, from described substrate desquamation, and will be peeled off to the silicon that obtains-graphene composite material and pulverized.
A kind of preparation method of lithium ion battery comprises the following steps:
Provide positive electrode active materials and negative active core-shell material, silicon-graphene composite material prepared by the preparation method that described negative active core-shell material is the described silicon-graphene composite material of claim 1 to 6 any one;
Respectively described positive electrode active materials and described negative active core-shell material are coated on plus plate current-collecting body and negative current collector and prepare positive pole and negative pole; And
By being soaked in electrolyte after described positive pole and negative pole and barrier film assembling, obtain lithium ion battery.
In embodiment, described positive electrode active materials is selected from least one in cobalt acid lithium, LiFePO4 and LiMn2O4 therein.
Therein in embodiment, prepared by following steps by described positive pole: described positive electrode active materials and anodal binding agent, anodal conductive agent are mixed to form to positive electrode in 75 ~ 90:5 ~ 10:5 ~ 15 in mass ratio, described positive electrode and solvent are mixed with to anode sizing agent, then described anode sizing agent is coated on plus plate current-collecting body, drying, rolls film, be made into positive pole after cutting.
Therein in embodiment, prepared by following steps by described negative pole: described negative active core-shell material, negative pole binding agent, cathode conductive agent are mixed to form to negative material in 80 ~ 90:5 ~ 10:5 ~ 10 in mass ratio, described negative material and solvent are mixed with to cathode size, then described cathode size is coated on negative current collector, drying, rolls film, be made into negative pole after cutting.
The preparation method of above-mentioned silicon-graphene composite material and the preparation method of lithium ion battery, utilize chemical vapour deposition technique to prepare silicon-graphene composite material, and technique is comparatively simple, simple to operate and consuming time shorter; Silicon-the graphene composite material of preparation is applied to the cycle performance that lithium ion battery can improve lithium ion battery.
The accompanying drawing explanation
The preparation method's of silicon-graphene composite material that Fig. 1 is an execution mode flow chart;
The preparation method's of the lithium ion battery that Fig. 2 is an execution mode flow chart.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the silicon-graphene composite material of an execution mode, comprise the steps:
Step S110, substrate is positioned over to the reative cell of chemical vapor depsotition equipment, under the protective gas atmosphere, it is 500 ℃ ~ 1300 ℃ that heated substrate makes substrate temperature.
Preferably, substrate is selected from a kind of in Copper Foil, iron foil and nickel foil.
Preferably, substrate was first used successively deionized water, ethanol and acetone ultrasonic cleaning post-drying before being positioned over reative cell.
Preferably, chemical vapor depsotition equipment is that hot-filament chemical vapor deposition equipment, radio frequency plasma strengthen chemical vapor depsotition equipment, microwave plasma enhanced chemical vapor depsotition equipment, laser chemical vapor deposition equipment, low pressure chemical vapor deposition equipment or aumospheric pressure cvd equipment.
Preferably, protective gas is nitrogen or argon gas.
Preferably, after substrate is positioned over to reative cell, in reative cell, pass into nitrogen, adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep 1 ~ 30min, stop afterwards logical nitrogen, the closure molecule pump, start substrate is heated.
Step S120, maintenance substrate temperature are 500 ℃ ~ 1300 ℃, in reative cell, pass into gaseous carbon source and gaseous state silicon source, the cooling silicon-graphene composite material that obtains after reaction 1min ~ 300min.
Preferably, gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
Preferably, gaseous state silicon source is selected from least one in tetramethylsilane and silicon tetrahydride.
Preferably, the mol ratio in gaseous carbon source and gaseous state silicon source is 0.5:1 ~ 6:1.
Preferably, the flow of gaseous carbon source is 50ml/min ~ 300ml/min, and the flow in gaseous state silicon source is 50ml/min 300ml/min.
In this step, carbon source is carried out chemical vapour deposition (CVD) and is generated Graphene, and the silicon source is carried out chemical vapour deposition (CVD) and generated silicon, and the silicon generated is distributed between graphene sheet layer uniformly.
Step S130, by silicon-graphene composite material from substrate desquamation, and will peel off the silicon that obtains-graphene composite material and pulverize.
Preferably, adopt ball mill that silicon-graphene composite material is crushed to silicon-graphene composite material and become micron order or nano level powder.
The preparation method of above-mentioned silicon-graphene composite material, utilize chemical vapour deposition technique to prepare silicon-graphene composite material, and technique is comparatively simple, simple to operate and consuming time shorter; In the silicon-graphene composite material of preparation, silicon is distributed between graphene sheet layer uniformly.
Refer to Fig. 2, the preparation method of the lithium ion battery of an execution mode, comprise the steps:
Step S210, positive electrode active materials and negative active core-shell material, negative active core-shell material are provided is silicon-graphene composite material.
Wherein, the preparation method of silicon-graphene composite material comprises the following steps:
Step S211, substrate is positioned over to the reative cell of chemical vapor depsotition equipment, under the protective gas atmosphere, it is 500 ℃ ~ 1300 ℃ that heated substrate makes substrate temperature.
Preferably, substrate is selected from a kind of in Copper Foil, iron foil and nickel foil.
Preferably, substrate was first used successively deionized water, ethanol and acetone ultrasonic cleaning post-drying before being positioned over reative cell.
Preferably, chemical vapor depsotition equipment is that hot-filament chemical vapor deposition equipment, radio frequency plasma strengthen chemical vapor depsotition equipment, microwave plasma enhanced chemical vapor depsotition equipment, laser chemical vapor deposition equipment, low pressure chemical vapor deposition equipment or aumospheric pressure cvd equipment.
Preferably, protective gas is nitrogen or argon gas.
Preferably, after substrate is positioned over to reative cell, in reative cell, pass into nitrogen, adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep 1 ~ 30min, stop afterwards logical nitrogen, the closure molecule pump, start substrate is heated.
Step S212, maintenance substrate temperature are 500 ℃ ~ 1300 ℃, in reative cell, pass into gaseous carbon source and gaseous state silicon source, the cooling silicon-graphene composite material that obtains after reaction 1min ~ 300min.
Preferably, gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
Preferably, gaseous state silicon source is selected from least one in tetramethylsilane and silicon tetrahydride.
Preferably, the mol ratio in gaseous carbon source and gaseous state silicon source is 0.5:1 ~ 6:1.
Preferably, the flow of gaseous carbon source is 50ml/min ~ 300ml/min, and the flow in gaseous state silicon source is 50ml/min ~ 300ml/min.
In this step, carbon source is carried out chemical vapour deposition (CVD) and is generated Graphene, and the silicon source is carried out chemical vapour deposition (CVD) and generated silicon, and the silicon generated is distributed between graphene sheet layer uniformly.
Step S213, by silicon-graphene composite material from substrate desquamation, and will peel off the silicon that obtains-graphene composite material and pulverize.
Preferably, adopt ball mill that silicon-graphene composite material is crushed to silicon-graphene composite material and become micron-sized powder.
Preferably, positive electrode active materials is selected from least one in cobalt acid lithium, LiFePO4 and LiMn2O4.
Step S220, respectively positive electrode active materials and negative active core-shell material are coated on plus plate current-collecting body and negative current collector and prepare positive pole and negative pole.
In present embodiment, positive electrode active materials, anodal adhesive, anodal conductive agent are mixed to form to positive electrode in 75 ~ 90:5 ~ 10:5 ~ 15 in mass ratio, positive electrode and solvent are formed to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.Anodal binding agent is Kynoar (PVDF), and anodal conductive agent is acetylene black.Solvent is 1-METHYLPYRROLIDONE (NMP).The viscosity of anode sizing agent is 4000 centipoises ~ 8000 centipoises, is preferably 5500 centipoises ~ 6500 centipoises.In present embodiment, negative electrode active material, negative pole binding agent, cathode conductive agent are mixed to form to negative material in 80 ~ 90:5 ~ 10:5 ~ 10 in mass ratio, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.The mixture that the negative pole binding agent is butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC), conductive agent is acetylene black.Solvent is 1-METHYLPYRROLIDONE (NMP).The viscosity of cathode size is 5500 centipoises ~ 6500 centipoises, is preferably 5500 centipoises ~ 6500 centipoises.
Step S230, by being soaked in electrolyte after positive pole and negative pole and barrier film assembling, obtain lithium ion battery.
In present embodiment, electrolyte is that lithium-ion electrolyte salt and non-aqueous organic solvent are formulated.Lithium-ion electrolyte salt is selected from LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2) and LiFSI (LiN (SO
2f)
2) at least one, non-aqueous organic solvent is selected from least one in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile.The concentration of electrolyte is preferably 1mol/L.
In present embodiment, anode pole piece, barrier film and cathode pole piece stack gradually rear composition battery core, seal battery core with lithium-ion battery shell again, finally by the liquid injection port be arranged on lithium-ion battery shell, inject electrolyte, the sealing liquid injection port can obtain lithium ion battery.
The preparation method of above-mentioned lithium ion battery is comparatively simple, and the cycle performance of the lithium ion battery of preparation is better.
Below in conjunction with specific embodiment, further illustrate.
Embodiment 1
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reative cell, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 1300 ℃, start to reative cell be filled with methane (flow: 100ml/ minute) and silicon tetrahydride (flow: mist 200ml/min minute), keep temperature-resistant, start to generate silicon/graphene composite material;
(4) after reacting 240 minutes, stop the substrate heating, and be cooled to room temperature, obtain silicon-graphene composite material.
Embodiment 2
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reative cell, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 1000 ℃, start to reative cell be filled with methane (flow: 100ml/ minute) and silicon tetrahydride (flow: mist 150ml/min minute), keep temperature-resistant, start to generate silicon/graphene composite material;
(4) after reacting 1 minute, stop the substrate heating, and be cooled to room temperature, obtain silicon/graphene composite material.
Embodiment 3
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reative cell, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and, after keeping 20 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 500 ℃, start to reative cell be filled with acetylene (flow: 50ml/ minute) and silicon tetrahydride (flow: mist 300ml/min minute), keep temperature-resistant, start to generate silicon/graphene composite material;
(4) after reacting 300 minutes, stop the substrate heating, and be cooled to room temperature, obtain silicon/graphene composite material.
Embodiment 4
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reative cell, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 800 ℃, start to reative cell be filled with ethene (flow: 300ml/ minute) and silicon tetrahydride (flow: mist 50ml/min minute), keep temperature-resistant, start to generate silicon/graphene composite material;
(4) after reacting 150 minutes, stop the substrate heating, and be cooled to room temperature, obtain silicon/graphene composite material.
Embodiment 5
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 1, cathode conductive agent acetylene black 80:10:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting; By positive electrode active materials cobalt acid lithium, anodal adhesive Kynoar, anodal conductive agent acetylene black in mass ratio 75:10:15 be mixed to form positive electrode, positive electrode and solvent 1-METHYLPYRROLIDONE are mixed to form to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.
(2) by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, then use battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is by LiPF subsequently
6be dissolved in dimethyl carbonate and form, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 6
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 2, cathode conductive agent acetylene black 90:5:5 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting; By iron phosphate serving as positive active material, anodal adhesive Kynoar, anodal conductive agent acetylene black in mass ratio 90:5:5 be mixed to form positive electrode, positive electrode and solvent 1-METHYLPYRROLIDONE are mixed to form to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.
(2) by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, then use battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is by LiBF subsequently
4be dissolved in diethyl carbonate and form, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 7
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 3, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting; By positive electrode active materials LiMn2O4, anodal adhesive Kynoar, anodal conductive agent acetylene black in mass ratio 80:5:15 be mixed to form positive electrode, positive electrode and solvent 1-METHYLPYRROLIDONE are mixed to form to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.
(2) by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in propene carbonate and is formed by LiTFSI, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 8
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 4, cathode conductive agent acetylene black 85:7:8 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting; By positive electrode active materials LiMn2O4, anodal adhesive Kynoar, anodal conductive agent acetylene black in mass ratio 85:5:10 be mixed to form positive electrode, positive electrode and solvent 1-METHYLPYRROLIDONE are mixed to form to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.
(2) by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in the mixed solvent be mixed to form by ethylene carbonate and acetonitrile and is formed by LiFSI, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 9
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 1, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.
(2) using the lithium sheet as positive pole, by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, then use battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is by LiPF subsequently
6be dissolved in dimethyl carbonate and form, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 10
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 2, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.
(2) using the lithium sheet as positive pole, by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in diethyl carbonate and is formed by LiBF4, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 11
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 3, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.
(2) using the lithium sheet as positive pole, by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in propene carbonate and is formed by LiTFSI, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 12
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 4, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.
(2) using the lithium sheet as positive pole, by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in the mixed solvent be mixed to form by ethylene carbonate and acetonitrile and is formed by LiFSI, the sealing liquid injection port, obtain lithium ion battery.
Refer to table 1, the lithium ion battery that table 1 is depicted as embodiment 9 ~ 12 preparations is discharged and recharged the test data of the stored energy capacitance obtained under the 0.1C electric current.
Table 1
As can be seen from Table 1, the capacity of lithium ion battery prepared by silicon-graphene composite material prepared by the present invention is higher, and the specific capacity conservation rate after 300 times that circulates all is greater than 65%, is up to 80%.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the preparation method of a silicon-graphene composite material, is characterized in that, comprises the steps:
Substrate is positioned over to the reative cell of chemical vapor depsotition equipment, under the protective gas atmosphere, heating described substrate, to make described substrate temperature be 500 ℃ ~ 1300 ℃; And
Pass into gaseous carbon source and gaseous state silicon source in described reative cell, the cooling silicon-graphene composite material that obtains after reaction 1min ~ 300min.
2. the preparation method of silicon-graphene composite material according to claim 1, is characterized in that, described protective gas is nitrogen or argon gas.
3. the preparation method of silicon-graphene composite material according to claim 1, is characterized in that, described gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
4. the preparation method of silicon-graphene composite material according to claim 1, is characterized in that, described gaseous state silicon source is selected from least one in tetramethylsilane and silicon tetrahydride.
5. the preparation method of silicon-graphene composite material according to claim 1, is characterized in that, the mol ratio in described gaseous carbon source and described gaseous state silicon source is 0.5:1 ~ 6:1.
6. the preparation method of silicon-graphene composite material according to claim 1, it is characterized in that, the preparation method of described silicon-graphene composite material also comprises step: described silicon-graphene composite material, from described substrate desquamation, and will be peeled off to the silicon that obtains-graphene composite material and pulverized.
7. the preparation method of a lithium ion battery, is characterized in that, comprises the following steps:
Provide positive electrode active materials and negative active core-shell material, silicon-graphene composite material prepared by the preparation method that described negative active core-shell material is the described silicon-graphene composite material of claim 1 to 6 any one;
Respectively described positive electrode active materials and described negative active core-shell material are coated on plus plate current-collecting body and negative current collector and prepare positive pole and negative pole; And
By being soaked in electrolyte after described positive pole and negative pole and barrier film assembling, obtain lithium ion battery.
8. the preparation method of lithium ion battery according to claim 7, is characterized in that, described positive electrode active materials is selected from least one in cobalt acid lithium, LiFePO4 and LiMn2O4.
9. the preparation method of lithium ion battery according to claim 7, it is characterized in that, prepared by following steps by described positive pole: described positive electrode active materials and anodal binding agent, anodal conductive agent are mixed to form to positive electrode in 75 ~ 90:5 ~ 10:5 ~ 15 in mass ratio, described positive electrode and solvent are mixed with to anode sizing agent, then described anode sizing agent is coated on plus plate current-collecting body, drying, rolls film, be made into positive pole after cutting.
10. the preparation method of lithium ion battery according to claim 7, it is characterized in that, prepared by following steps by described negative pole: described negative active core-shell material, negative pole binding agent, cathode conductive agent are mixed to form to negative material in 80 ~ 90:5 ~ 10:5 ~ 10 in mass ratio, described negative material and solvent are mixed with to cathode size, then described cathode size is coated on negative current collector, drying, rolls film, be made into negative pole after cutting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101765853A CN103456926A (en) | 2012-05-31 | 2012-05-31 | Preparation methods of silicon-graphene composite material and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101765853A CN103456926A (en) | 2012-05-31 | 2012-05-31 | Preparation methods of silicon-graphene composite material and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103456926A true CN103456926A (en) | 2013-12-18 |
Family
ID=49739071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101765853A Pending CN103456926A (en) | 2012-05-31 | 2012-05-31 | Preparation methods of silicon-graphene composite material and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103456926A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794761A (en) * | 2014-01-15 | 2014-05-14 | 合肥国轩高科动力能源股份公司 | Preparation method of silicon/lithium titanate composite negative electrode material of lithium ion battery |
| CN109256534A (en) * | 2017-07-12 | 2019-01-22 | 赢创德固赛有限公司 | Silico-carbo composite powder |
| CN111969186A (en) * | 2020-07-22 | 2020-11-20 | 自贡兴川储能技术有限公司 | Silicon-carbon film cathode with graphene as framework and preparation method thereof |
| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| US11633785B2 (en) | 2019-04-30 | 2023-04-25 | 6K Inc. | Mechanically alloyed powder feedstock |
| US11717886B2 (en) | 2019-11-18 | 2023-08-08 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
| US11839919B2 (en) | 2015-12-16 | 2023-12-12 | 6K Inc. | Spheroidal dehydrogenated metals and metal alloy particles |
| US11855278B2 (en) | 2020-06-25 | 2023-12-26 | 6K, Inc. | Microcomposite alloy structure |
| US11919071B2 (en) | 2020-10-30 | 2024-03-05 | 6K Inc. | Systems and methods for synthesis of spheroidized metal powders |
| US11963287B2 (en) | 2020-09-24 | 2024-04-16 | 6K Inc. | Systems, devices, and methods for starting plasma |
-
2012
- 2012-05-31 CN CN2012101765853A patent/CN103456926A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794761A (en) * | 2014-01-15 | 2014-05-14 | 合肥国轩高科动力能源股份公司 | Preparation method of silicon/lithium titanate composite negative electrode material of lithium ion battery |
| US11839919B2 (en) | 2015-12-16 | 2023-12-12 | 6K Inc. | Spheroidal dehydrogenated metals and metal alloy particles |
| CN109256534A (en) * | 2017-07-12 | 2019-01-22 | 赢创德固赛有限公司 | Silico-carbo composite powder |
| CN109256534B (en) * | 2017-07-12 | 2024-01-26 | 赢创运营有限公司 | Silicon-carbon composite powder |
| US11633785B2 (en) | 2019-04-30 | 2023-04-25 | 6K Inc. | Mechanically alloyed powder feedstock |
| US11717886B2 (en) | 2019-11-18 | 2023-08-08 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| US11855278B2 (en) | 2020-06-25 | 2023-12-26 | 6K, Inc. | Microcomposite alloy structure |
| CN111969186A (en) * | 2020-07-22 | 2020-11-20 | 自贡兴川储能技术有限公司 | Silicon-carbon film cathode with graphene as framework and preparation method thereof |
| CN111969186B (en) * | 2020-07-22 | 2021-09-28 | 自贡兴川储能技术有限公司 | Silicon-carbon film cathode with graphene as framework and preparation method thereof |
| US11963287B2 (en) | 2020-09-24 | 2024-04-16 | 6K Inc. | Systems, devices, and methods for starting plasma |
| US11919071B2 (en) | 2020-10-30 | 2024-03-05 | 6K Inc. | Systems and methods for synthesis of spheroidized metal powders |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103456926A (en) | Preparation methods of silicon-graphene composite material and lithium ion battery | |
| CN105489855B (en) | High capacity type lithium ion battery nucleocapsid silicon-carbon composite cathode material and preparation method thereof | |
| CN111354939B (en) | Porous silicon composite material and preparation method and application thereof | |
| CN104617259A (en) | Method for protective treatment of lithium cathodes in lithium secondary batteries | |
| CN105762360A (en) | Graphene-silicon-coated composite negative electrode material and preparing method and application thereof | |
| CN103700808A (en) | Lithium ion battery composite anode pole piece, preparation method and lithium ion battery | |
| CN104064736A (en) | Carbon nanotube/silicon/graphene composite material, preparation method thereof and lithium ion battery | |
| CN110668509A (en) | Selenium-coated high-nickel ternary layered positive electrode material and preparation method thereof | |
| WO2018094773A1 (en) | Gel-polymer electrolyte power battery | |
| CN103515587A (en) | Preparation methods of lithium titanate-graphene composite material and lithium ion battery | |
| CN107359302A (en) | Nitrogenize carbon composite and preparation method and application | |
| CN108417777A (en) | A kind of porous triple anode composite piece and preparation method thereof and its application | |
| CN101420047A (en) | Preparation of lithium sulfureous secondary battery | |
| CN104617272A (en) | Method for preparing porous silicon-carbon composite material | |
| CN103000939A (en) | Lithium ion battery with graphene composite membrane as current collector and preparation method thereof | |
| WO2018059180A1 (en) | High-power, high-energy chemical power supply and preparation method therefor | |
| CN103456937A (en) | Preparation methods of lithium titanate-graphene composite material and lithium ion battery | |
| CN102569788A (en) | Lithium ion battery anode material and preparation method thereof, and lithium ion battery | |
| CN103730658A (en) | Silicon and graphene composite material, preparing method thereof and lithium ion battery | |
| CN110943207B (en) | Modified TiNb2O7Material and modification method | |
| CN113823781A (en) | Composite negative electrode material and preparation method thereof | |
| CN115072703A (en) | Composite negative electrode material and preparation method and application thereof | |
| CN104064755B (en) | Cobaltosic oxide-graphene-carbon nano tube composite material and its preparation method and application | |
| CN114094070A (en) | Titanium niobate-coated hard carbon composite material and preparation method thereof | |
| CN109244335A (en) | A kind of polyimide diaphragm lithium-sulfur cell 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131218 |
|
| WD01 | Invention patent application deemed withdrawn after publication |