CN114975945A - Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN114975945A CN114975945A CN202210653482.5A CN202210653482A CN114975945A CN 114975945 A CN114975945 A CN 114975945A CN 202210653482 A CN202210653482 A CN 202210653482A CN 114975945 A CN114975945 A CN 114975945A
- Authority
- CN
- China
- Prior art keywords
- carbon
- silicon
- lithium ion
- negative electrode
- ion battery
- 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
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 19
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002861 polymer material Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 17
- 239000007833 carbon precursor Substances 0.000 claims description 16
- 239000010405 anode material Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011300 coal pitch Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229920005546 furfural resin Polymers 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000010000 carbonizing Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002153 silicon-carbon composite material Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical compound [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- YNIXPIABGHKZPS-UHFFFAOYSA-N [C].CC Chemical compound [C].CC YNIXPIABGHKZPS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- -1 polyethylene propylene Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
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
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof are disclosed, the negative electrode material is a core-shell structure formed by an inner core and a shell coated on the surface of the inner core, the inner core is a complex formed by silica/carbon nano tube/amorphous carbon A, the shell is amorphous carbon B, and the mass ratio of the inner core to the shell is (90-99): (1-10), the thickness of the shell is 10-500 nm; the preparation method comprises the steps of uniformly mixing the silicon oxide material, the carbon nano tube, the polymer material and the additive thereof, briquetting the mixture, carbonizing the mixture in an inert atmosphere, crushing the carbonized mixture, adding the catalyst, and depositing the amorphous carbon layer on the surface of the carbonized mixture by a chemical vapor deposition method. According to the invention, the inner core is doped with the carbon nano tube and the amorphous carbon thereof to coat silica, so that the expansion is reduced, the conductivity of the material is improved, and meanwhile, the outer layer is coated with a carbon layer with higher density, so that the synergistic effect of the double carbon layers is exerted, the expansion is reduced, and the rate capability of the material is improved.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof.
Background
The silicon carbon material is a preferred material of the next generation of high energy density lithium ion battery due to the advantages of high energy density, wide material source and the like, but the material has poor conductivity, low first efficiency and large expansion in the charging and discharging processes, so that the cycle performance and the rate performance of the material are poor, one of the measures for improving the conductivity of the silicon carbon material is to improve the conductivity of the material and improve the quick charging performance of the material by doping and coating the surface of the material, but the expansion of the material is still large, which can influence the cycle performance of the battery and the battery grouping of the battery.
At present, there are many measures for reducing the expansion of silicon carbon materials, such as nanocrystallization of materials, porous silicon carbon, carbon nanotubes with high doped mechanical strength, and the like. However, the nano silicon carbon has the problems of low initial efficiency, deviation of safety performance, deterioration of later performance of cycle performance, easy water jump of a battery and the like due to strong material activity.
Disclosure of Invention
The invention aims to provide a silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the silicon-carbon negative electrode material for the lithium ion battery is of a core-shell structure and comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is a composite body formed by silica/carbon nano tube/amorphous carbon A, the shell is amorphous carbon B, and the mass ratio of the inner core to the shell is (90-99): (1-10), the thickness of the shell is 10-500 nm.
Further, the mass ratio of the silicon oxygen to the carbon nano tubes to the amorphous carbon A in the composite body is (60-80): (1-5): (20-40).
Further, the amorphous carbon A is formed by carbonization pyrolysis of a polymer.
Further, the amorphous carbon B is formed by hydrocarbon cracking.
Further, the shell contains 0.01-0.5 wt% of catalyst, and the catalyst is one or more of nano iron, nano cobalt, nano nickel and iron chloride, cobalt chloride or nickel chloride.
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) preparing a silicon-carbon precursor A:
according to the mass ratio of 60-80: 1-5: 20-40: weighing 0.5-2 parts of silica, carbon nanotube powder, a polymer material and an additive, ball-milling for 12-72 h, briquetting under the pressure of 10-25MPa, and heating to 300-600 ℃ under an inert atmosphere for melting carbonization to obtain a silicon-carbon precursor A;
(2) preparing a silicon-carbon negative electrode material:
and (2) crushing the silicon-carbon precursor A to the particle size of 1-10 microns, adding 0.1-1 wt% of catalyst powder, uniformly mixing, transferring to a tubular furnace, heating to 700-1000 ℃ under an inert atmosphere, introducing a carbon source gas for chemical vapor deposition for 1-12 hours, stopping introducing the carbon source gas, introducing the inert gas for cooling, and crushing to obtain the silicon-carbon cathode material.
Further, the ball milling conditions in the step (1) are as follows: the ratio of the balls to the material is (20-40) to (60-80), and the rotation speed is 40-80 rpm.
Further, in the step (1), the polymer material is one or more of coal pitch, coal tar, phenolic resin, epoxy resin, furfural resin and polyacrylonitrile.
Further, in the step (1), the additive is one or more of ferric chloride, silicon carbide, boron carbide and vanadium oxide, and the particle size D50 is 1-10 mu m.
Further, in the step (2), the carbon source gas is any one of methane, acetylene and ethylene.
The invention has the beneficial effects that:
1. according to the silicon-carbon negative electrode material, the carbon nano tube and the amorphous carbon thereof are doped in the inner core to coat silica, so that the expansion of the material is reduced, the conductivity of the material is improved, meanwhile, a carbon layer with higher density is further coated on the outer layer, the synergistic effect of the double carbon layers is exerted, the expansion of the material is reduced, and the rate capability of the material is improved.
2. The silicon-carbon cathode material ensures the bonding strength and the dispersion uniformity of the inner core silica, the carbon nano tube and the amorphous carbon in the preparation process, improves the tap density and the electronic conductivity of the silica, further reduces the volume expansion effect of the silica in the charging and discharging processes, and simultaneously improves the electronic conductivity of the material when the carbon nano tube is uniformly dispersed in the amorphous carbon to form a network structure so as to reduce the expansion of the silica.
3. The carbon layer deposited on the surface of the outer shell of the silicon-carbon negative electrode material by adopting a vapor deposition method in the preparation process has the characteristics of high density and high conductivity, and the synergistic effect between the amorphous carbon which is formed by coating a layer of polymer material with good flexibility and formed after carbonizing and the amorphous carbon formed after gas cracking on the silicon-carbon material can restrict the initial expansion and the cyclic expansion of the silicon-carbon in the charging and discharging process on one hand, and on the other hand, the carbon layer with the density deposited on the outermost layer can prevent the electrolyte from directly contacting with the core silicon, thereby improving the cycle and power performance of the material.
Drawings
Fig. 1 is an SEM image of the silicon carbon anode material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
(1) Preparing a silicon-carbon precursor A:
weighing 70g of silicon-oxygen material, 3g of carbon nanotube powder material, 27g of coal tar pitch and 1g of ferric chloride material (granularity D50=5μm), ball-milling for 48h at the speed of 60rpm according to the ball-to-material ratio of 30:70, then transferring to a briquetting machine, briquetting under the pressure of 20MPa, and heating to 500 ℃ under the argon inert atmosphere for melting and carbonizing to obtain a silicon-carbon precursor A.
(2) Preparing a silicon-carbon negative electrode material:
and crushing the obtained 100g of silicon-carbon precursor A until the granularity is 5 mu m, adding 0.5g of nano iron catalyst powder, uniformly mixing, transferring to a tubular furnace, heating to 800 ℃ under an argon inert atmosphere, introducing a methane carbon source gas for chemical vapor deposition for 6 hours, stopping introducing the carbon source gas, introducing the argon inert gas for cooling, and crushing to obtain the silicon-carbon cathode material.
Fig. 1 is an SEM image of the silicon carbon anode material prepared in this example.
Example 2
(2) Preparing a silicon-carbon precursor A:
60g of silicon oxygen material, 1g of carbon nanotube powder material, 39g of phenolic resin and 0.5g of silicon carbide material (D50 =1 mu m) are weighed, ball milling is carried out for 72h at the speed of 40rpm according to the ball-to-material ratio of 20: 80, then the mixture is transferred to a briquetting machine to be briquetted under the pressure of 10MPa, and the mixture is heated to 300 ℃ under the argon inert atmosphere to be subjected to melting carbonization, so that a silicon-carbon precursor A is obtained.
(2) Preparing a silicon-carbon negative electrode material:
and (2) crushing 100g of the obtained silicon-carbon precursor A until the granularity is 1 mu m, adding 0.1g of catalyst powder of nano cobalt (the particle size is 10 nm), uniformly mixing, transferring to a tubular furnace, heating to 700 ℃ under an argon inert atmosphere, introducing acetylene carbon source gas for chemical vapor deposition for 12 hours, stopping introducing the carbon source gas, changing the inert gas into the carbon source gas, cooling, and crushing to obtain the silicon-carbon cathode material.
Example 3
(1) Preparing a silicon-carbon precursor A:
weighing 80g of silica material, 5g of carbon nanotube powder material, 15g of polyacrylonitrile material and 2g of boron carbide material (D50 =10 mu m), ball-milling for 12h at the speed of 80rpm according to the ball-to-material ratio of 40:60, then transferring to a briquetting machine, briquetting under the pressure of 25MPa, and heating to 600 ℃ under the argon inert atmosphere for melting and carbonizing to obtain a silicon-carbon precursor A.
(2) Preparing a silicon-carbon negative electrode material:
and (2) crushing 100g of the obtained silicon-carbon precursor A until the granularity is 10 mu m, adding 1g of nano nickel (with the particle size of 500 nm) catalyst powder, uniformly mixing, then transferring to a tubular furnace, heating to 1000 ℃ under the inert atmosphere of argon, introducing ethane carbon source gas for chemical vapor deposition for 1h, then stopping introducing the carbon source gas, introducing inert gas for cooling, and crushing to obtain the silicon-carbon cathode material.
Comparative example:
weighing 70g of silica material, 3g of carbon nanotube powder material and 27g of coal pitch, ball-milling for 48 hours at the speed of 60rpm according to the ball-to-material ratio of 30:70, and then heating to 500 ℃ under the inert atmosphere of argon gas for melting carbonization to obtain a silicon-carbon precursor A; and then transferring the silicon carbide anode material to a tubular furnace, heating the silicon carbide anode material to 800 ℃ under the inert atmosphere of argon, introducing a methane carbon source gas for chemical vapor deposition for 6 hours, stopping introducing the carbon source gas, introducing the inert gas of argon for cooling, and crushing to obtain the silicon carbide anode material.
And (3) performance testing:
(1) physical and chemical properties and button cell test: negative electrode materials obtained in examples 1 to 3 and comparative example were assembled into a button cell, and examples 1 to 3 were named a1, a2 and A3, respectively, and comparative example was named B1.
The button cell preparation method comprises the following steps: adding a binder, a conductive agent and a solvent into the negative electrode materials (namely, the silicon-carbon composite materials) obtained in the examples 1-3 and the comparative example, stirring and pulping, coating the negative electrode materials on copper foil, and drying and rolling to obtain a negative electrode sheet; the used binder is LA132 binder (specifically: a cross-linked product of acrylonitrile and polyacrylic acid, the molecular weight is 10 ten thousand), the conductive agent SP (super carbon black), the solvent is secondary distilled water, and the negative electrode material is SP: LA132: secondary distilled water =95g:1g:4g:220 mL; the electrolyte adopted by the button cell is LiPF 6 Ethylene carbonate EC + diethyl carbonate DEC (1:1), wherein a metal lithium sheet is used as a counter electrode, and a diaphragm is a polyethylene propylene (PEP) composite film; the simulated battery is assembled in a glove box filled with hydrogen, the electrochemical performance is carried out on a Wuhan blue electricity Xinwei 5V/10mA type battery tester, the charging and discharging voltage range is 0.005V to 2.0V, and the charging and discharging speed is 0.1C.
The results of the battery tests on the button cells are shown in table 1.
Table 1 button cell of examples and comparative examples and comparison of physicochemical parameters thereof
(2) Pouch cell testing
The silicon-carbon composite materials obtained in examples 1 to 3 and the comparative example were doped with 90wt% of artificial graphite as a negative electrode material (the silicon-carbon composite material accounts for 10 wt%) to prepare a negative electrode piece, NCM811 was used as a positive electrode material, and LiPF was used 6 The method comprises the following steps of preparing a 5Ah soft package battery by taking/EC + DEC (volume ratio 1:1) as electrolyte and a Celgard 2400 membrane as a diaphragm, wherein the negative pole pieces obtained in examples 1-3 are respectively named as C1, C2 and C3, the soft package batteries prepared by the negative pole pieces obtained in examples 1-3 are respectively named as C ' 1, C ' 2 and C ' 3, and the negative pole pieces obtained in comparative examples 1-3 are respectively named as D1; the soft package batteries prepared by the negative pole piece obtained by the comparison example are respectively named as D' 1;
and (3) testing the liquid absorption speed of the obtained negative pole piece, wherein the testing method comprises the following steps: absorbing 5mL of electrolyte by using a 10mL pipette, then dropwise adding the electrolyte to the surface of the negative pole piece, and observing the drying time of the electrolyte, namely the imbibing speed;
and testing the liquid retention capacity of the obtained negative pole piece, wherein the testing method comprises the following steps: the ratio of the electrolyte amount of 24 h/the electrolyte amount of 0h is calculated to obtain the ratio;
testing the pole piece rebound of the obtained negative pole piece, wherein the testing method comprises the following steps: the initial thickness D1 of the pole piece is tested, then the thickness D2 of the pole piece after the battery is rolled is tested, and then the rebound rate = (D2-D1)/D1 is calculated.
The test results are shown in table 2, the cycle performance test (voltage is 2.8-4.2V, and charge-discharge rate is 1C/1C) of the soft package battery is performed, and the charge-discharge DCR of the battery is also tested, and the test results are shown in table 3.
TABLE 2 comparison of Pole piece parameters for examples and comparative examples
TABLE 3 comparison of cycling performance of pouch cells
It can be seen from table 1 that the discharge capacity and efficiency of the rechargeable battery made of the negative electrode materials obtained in examples 1-3 are significantly higher than those of comparative example 1, the silicon-carbon composite negative electrode material of the present invention can provide a battery with good discharge capacity and efficiency, the silicon-carbon negative electrode material adopts a briquetting method to provide a high compactness, the tap density of the material is increased, the impedance is reduced, and thus the capacity and the first efficiency of the material are increased.
As can be seen from table 2, the liquid absorbing and retaining capabilities of the negative electrode materials obtained in examples 1 to 3 are significantly higher than those of comparative example 1, which indicates that the silicon-carbon composite negative electrode material of the present invention has higher liquid absorbing and retaining capabilities, and the material has a higher specific surface area and a larger number of structural holes formed by the material under the action of the catalyst, so that the liquid absorbing and retaining capabilities of the material are improved; the rebound rate of the negative pole piece prepared by the silicon-carbon composite negative pole material obtained in the embodiment 1-3 is obviously lower than that of the negative pole piece prepared by the comparative example 1, which shows that the negative pole piece prepared by the silicon-carbon composite negative pole material has lower rebound rate, because: the materials of the examples have high tap density and good contact between the materials, and restrict the expansion of lithium ions in the charge and discharge process.
As can be seen from table 3, the cycle performance of the pouch battery obtained by using the silicon-carbon composite negative electrode materials of examples 1 to 3 is significantly better than that of the pouch battery obtained by using the negative electrode material of the comparative example, which is the bonding strength and dispersion uniformity of the core silica, the carbon nanotube and the amorphous carbon, improves the tap density and the electronic conductivity thereof, reduces the volume expansion effect of silica in the charging and discharging processes, and improves the cycle performance; meanwhile, the carbon nano tubes are uniformly dispersed in the amorphous carbon to form a network structure, so that the expansion of silica is reduced, the electronic conductivity of the material is improved, and the impedance is reduced.
It should be noted that the above embodiments are only for illustrating the present invention, but the present invention is not limited to the above embodiments, and any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention fall within the protection scope of the present invention.
Claims (10)
1. The silicon-carbon negative electrode material for the lithium ion battery is characterized by being of a core-shell structure and comprising an inner core and a shell coated on the surface of the inner core, wherein the inner core is a composite body consisting of silica/carbon nano tube/amorphous carbon A, the shell is amorphous carbon B, and the mass ratio of the inner core to the shell is (90-99): (1-10), the thickness of the shell is 10-500 nm.
2. The silicon-carbon negative electrode material for the lithium ion battery as claimed in claim 1, wherein the mass ratio of the silicon oxide, the carbon nanotubes and the amorphous carbon A in the composite is (60-80): (1-5): (20-40).
3. The silicon-carbon negative electrode material for lithium ion batteries according to claim 1, wherein the amorphous carbon A is formed by carbonization and pyrolysis of a polymer.
4. The silicon-carbon anode material for lithium ion batteries according to claim 1, wherein the amorphous carbon B is formed by hydrocarbon cracking.
5. The silicon-carbon anode material for the lithium ion battery as claimed in claim 1, wherein the shell contains 0.01-0.5 wt% of a catalyst, and the catalyst is one or more of nano iron, nano cobalt, nano nickel, iron chloride, cobalt chloride or nickel chloride.
6. The preparation method of the silicon-carbon anode material for the lithium ion battery as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) preparing a silicon-carbon precursor A:
according to the mass ratio of 60-80: 1-5: 20-40: weighing 0.5-2 parts of silica, carbon nanotube powder, a polymer material and an additive, ball-milling for 12-72 h, briquetting under the pressure of 10-25MPa, and heating to 300-600 ℃ under an inert atmosphere for melting carbonization to obtain a silicon-carbon precursor A;
(2) preparing a silicon-carbon negative electrode material:
and (2) crushing the silicon-carbon precursor A to the particle size of 1-10 microns, adding 0.1-1 wt% of catalyst powder, uniformly mixing, transferring to a tubular furnace, heating to 700-1000 ℃ under an inert atmosphere, introducing a carbon source gas for chemical vapor deposition for 1-12 hours, stopping introducing the carbon source gas, introducing the inert gas for cooling, and crushing to obtain the silicon-carbon cathode material.
7. The preparation method of the silicon-carbon negative electrode material for the lithium ion battery as claimed in claim 6, wherein the ball milling conditions in the step (1) are as follows: the ball material ratio is 20-40: 60-80, and the rotating speed is 40-80 rpm.
8. The method for preparing the silicon-carbon anode material for the lithium ion battery according to claim 6, wherein in the step (1), the polymer material is one or more of coal pitch, coal tar, phenolic resin, epoxy resin, furfural resin and polyacrylonitrile.
9. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 6, wherein in the step (1), the additive is one or more of ferric chloride, silicon carbide, boron carbide and vanadium oxide, and the particle size D50 is 1-10 μm.
10. The method for preparing the silicon-carbon anode material for the lithium ion battery according to claim 6, wherein in the step (2), the carbon source gas is any one of methane, acetylene and ethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210653482.5A CN114975945A (en) | 2022-06-10 | 2022-06-10 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210653482.5A CN114975945A (en) | 2022-06-10 | 2022-06-10 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114975945A true CN114975945A (en) | 2022-08-30 |
Family
ID=82962555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210653482.5A Pending CN114975945A (en) | 2022-06-10 | 2022-06-10 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114975945A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496701A (en) * | 2011-11-24 | 2012-06-13 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon alloy cathode material used in lithium ion battery, and preparation method thereof |
| CN103474667A (en) * | 2013-08-16 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN108807861A (en) * | 2017-05-03 | 2018-11-13 | 安普瑞斯（南京）有限公司 | A kind of Si-C composite material and preparation method thereof for lithium ion battery |
| CN110112378A (en) * | 2019-04-02 | 2019-08-09 | 深圳市三顺纳米新材料股份有限公司 | Lithium ion battery silicon oxygen composite negative pole material and preparation method thereof |
| CN110504435A (en) * | 2019-08-30 | 2019-11-26 | 石家庄尚太科技有限公司 | A kind of method that low temperature plasma prepares silicon-carbon composite cathode material |
| KR20200083808A (en) * | 2018-12-28 | 2020-07-09 | 강원대학교산학협력단 | Silicon-carbon composite negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery including the same |
| CN111755677A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Core-shell structure porous silicon negative electrode material for lithium ion battery and preparation method thereof |
| CN113964307A (en) * | 2021-10-24 | 2022-01-21 | 江苏载驰科技股份有限公司 | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof |
| CN114122357A (en) * | 2021-11-10 | 2022-03-01 | 云南中晟新材料有限责任公司 | Lithium salt-coated graphene-doped silicon-carbon composite material and preparation method thereof |
| CN114447305A (en) * | 2022-01-29 | 2022-05-06 | 辽宁中宏能源新材料股份有限公司 | Multi-element carbon-based rapid-charging negative electrode composite material and preparation method thereof |
| CN114447304A (en) * | 2022-01-28 | 2022-05-06 | 蜂巢能源科技股份有限公司 | Hard carbon composite negative electrode material and preparation method and application thereof |
-
2022
- 2022-06-10 CN CN202210653482.5A patent/CN114975945A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496701A (en) * | 2011-11-24 | 2012-06-13 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon alloy cathode material used in lithium ion battery, and preparation method thereof |
| CN103474667A (en) * | 2013-08-16 | 2013-12-25 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN108807861A (en) * | 2017-05-03 | 2018-11-13 | 安普瑞斯（南京）有限公司 | A kind of Si-C composite material and preparation method thereof for lithium ion battery |
| KR20200083808A (en) * | 2018-12-28 | 2020-07-09 | 강원대학교산학협력단 | Silicon-carbon composite negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery including the same |
| CN110112378A (en) * | 2019-04-02 | 2019-08-09 | 深圳市三顺纳米新材料股份有限公司 | Lithium ion battery silicon oxygen composite negative pole material and preparation method thereof |
| CN110504435A (en) * | 2019-08-30 | 2019-11-26 | 石家庄尚太科技有限公司 | A kind of method that low temperature plasma prepares silicon-carbon composite cathode material |
| CN111755677A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Core-shell structure porous silicon negative electrode material for lithium ion battery and preparation method thereof |
| CN113964307A (en) * | 2021-10-24 | 2022-01-21 | 江苏载驰科技股份有限公司 | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof |
| CN114122357A (en) * | 2021-11-10 | 2022-03-01 | 云南中晟新材料有限责任公司 | Lithium salt-coated graphene-doped silicon-carbon composite material and preparation method thereof |
| CN114447304A (en) * | 2022-01-28 | 2022-05-06 | 蜂巢能源科技股份有限公司 | Hard carbon composite negative electrode material and preparation method and application thereof |
| CN114447305A (en) * | 2022-01-29 | 2022-05-06 | 辽宁中宏能源新材料股份有限公司 | Multi-element carbon-based rapid-charging negative electrode composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄丽主编: "聚合物复合材料", 北京：中国轻工业出版社, pages: 88 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107492645B (en) | Silicon oxide-graphene composite material and preparation method thereof | |
| WO2022166059A1 (en) | Boron-doped resin-coated artificial graphite material | |
| CN114447305B (en) | Multi-carbon-based quick-charge anode composite material and preparation method thereof | |
| CN109037643B (en) | High-capacity high-compaction graphite composite material and preparation method thereof | |
| CN113764644B (en) | Quick-filling composite graphite material and preparation method thereof | |
| CN114122391B (en) | High-power graphite composite material and preparation method thereof | |
| CN114824238B (en) | Preparation method and application of high specific capacity silicon-carbon anode material functionalized based on polyethyleneimine and polydopamine copolymer | |
| CN114843482B (en) | Core-shell type silicon-carbon composite material and preparation method and application thereof | |
| CN114655951A (en) | Preparation method of lithium ion battery negative electrode material | |
| CN114300671A (en) | Graphite composite negative electrode material and preparation method and application thereof | |
| CN113889595A (en) | Preparation method of solid electrolyte coated graphite composite material | |
| CN113594461B (en) | Carbon-silicon composite material and preparation method and application thereof | |
| CN114975974A (en) | High-energy-density graphite composite material, preparation method thereof and lithium ion battery | |
| CN115714177A (en) | Silicon-carbon composite material and preparation method thereof | |
| CN114899384A (en) | Three-dimensional porous silica anode composite material and preparation method thereof | |
| CN114843480A (en) | Silicon-phosphorus co-doped hard carbon composite material and preparation method and application thereof | |
| CN115172680A (en) | High-capacity high-rate lithium ion battery and preparation method thereof | |
| CN114975945A (en) | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN114447304A (en) | Hard carbon composite negative electrode material and preparation method and application thereof | |
| CN115332496B (en) | Preparation method of silica composite material for lithium ion battery | |
| CN115893400B (en) | Preparation method of negative electrode material for long-cycle lithium ion battery | |
| CN115241526A (en) | Artificial graphite composite material and preparation method thereof | |
| CN116805677A (en) | Silicon-carbon composite material, preparation method thereof and lithium ion battery | |
| CN117154044A (en) | High-power graphite composite material and preparation method and application thereof | |
| CN117276496A (en) | High-energy-density quick-filling alloy graphite composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |