CN114843482A - Core-shell silicon-carbon composite material and preparation method and application thereof - Google Patents
Core-shell silicon-carbon composite material and preparation method and application thereof Download PDFInfo
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- CN114843482A CN114843482A CN202210567480.4A CN202210567480A CN114843482A CN 114843482 A CN114843482 A CN 114843482A CN 202210567480 A CN202210567480 A CN 202210567480A CN 114843482 A CN114843482 A CN 114843482A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 42
- 239000011258 core-shell material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000010416 ion conductor Substances 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002210 silicon-based material Substances 0.000 claims abstract description 21
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000007740 vapor deposition Methods 0.000 claims abstract description 15
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 229920002472 Starch Polymers 0.000 claims abstract description 10
- 239000008107 starch Substances 0.000 claims abstract description 8
- 235000019698 starch Nutrition 0.000 claims abstract description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000003610 charcoal Substances 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 claims description 2
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
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- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- HRNWETBDIWJQRN-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) hexanethioate Chemical compound CCCCCC(=O)SCCC[Si](OCC)(OCC)OCC HRNWETBDIWJQRN-UHFFFAOYSA-N 0.000 claims description 2
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 34
- 238000007599 discharging Methods 0.000 abstract description 10
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- 230000007547 defect Effects 0.000 abstract description 7
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- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000005543 nano-size silicon particle Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
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- 239000011230 binding agent Substances 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 101150058243 Lipf gene Proteins 0.000 description 2
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
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- 239000007770 graphite material Substances 0.000 description 2
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- 229940100445 wheat starch Drugs 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 1
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- 244000017020 Ipomoea batatas Species 0.000 description 1
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- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
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Abstract
The embodiment of the invention discloses a core-shell silicon-carbon composite material, wherein a core is a composite material comprising hard carbon, amorphous carbon and silicon-based material components, and a shell is a fast ion conductor; wherein the silicon-based material is a mixture of silicon monoxide and silicon powder, and the mass ratio of the silicon-based material to the silicon oxide is 1: 0.02-0.2; the composite material is prepared by mixing, ball-milling and reacting the raw materials of the silicon monoxide, the silicon powder, the silane coupling agent and the starch, spraying and drying the mixture to obtain a kernel, and then depositing the fast ion conductor on the surface of the kernel by an atomic vapor deposition method to obtain the core-shell silicon-carbon composite material. According to the core-shell silicon-carbon composite material, the specific capacity of the silicon-based material is increased, and the silicon-based material is embedded into hard carbon to reduce expansion in the charging and discharging processes; the shell is a fast ion conductor, the fast charging performance of the material is improved, the fast ion conductor is coated on the surface of the inner core by adopting an atomic vapor deposition method, the defects on the surface of the inner core are greatly reduced, and the first efficiency of the material is improved.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a core-shell silicon-carbon composite material and a preparation method and application thereof.
Background
The hard carbon material is used as one of the choices of the fast-charging negative electrode material with the advantages of good fast-charging performance (the interlayer spacing is more than or equal to 0.38nm), good safety performance (the voltage platform is 0.2V), zero expansion, wide material sources (can be coconut shells, starch, asphalt, resin and other carbon-containing compounds) and the like, and is applied to the fast-charging lithium ion battery and the sodium ion battery, but the hard carbon has the defect of low specific capacity (300Ah/g), is lower than the specific capacity (355Ah/g) of a marketable graphite material, has the primary efficiency of only 80 percent and is far lower than the primary efficiency of 92-94 percent of the graphite material.
The theoretical specific capacity of the silicon material is 4200Ah/g, but the defect that the full-electricity expansion rate is high (300%) exists, so that the silicon material is easy to collapse in a crystal structure in a circulating process, the conductive network structure of an electrode is damaged, and the service life of a battery is further greatly shortened; meanwhile, silicon is a semiconductor material, and has extremely poor conductivity, thereby affecting the rate characteristics of the battery. Therefore, silicon cannot be independently used as a negative electrode material, and at present, the volume expansion is relieved mainly by forming a silicon-carbon composite material by using nano silicon and a carbon-based material, so that the cycle and rate characteristics of the material are improved. Although general silicon-carbon composite materials are improved in energy density and rate capability, the defects of low initial efficiency and the like still exist, so that the silicon-carbon composite materials which have both energy density and quick charging performance and can improve the initial efficiency of the materials need to be developed.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the core-shell silicon-carbon composite material, the energy density is improved and the bound expansion is realized by doping the silicon-based material in the porous hard carbon, and meanwhile, the fast ion conductor material coated on the outer layer improves the insertion and extraction rate of lithium ions in the charging and discharging process on one hand, and reduces the side reaction of the fast ion conductor material coated on the outer surface on the other hand, so that the first efficiency is improved.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the technical purpose of the first aspect of the invention is to provide a core-shell silicon-carbon composite material, wherein the core is a composite material comprising hard carbon, amorphous carbon and silicon-based material components, and the shell is a fast ion conductor; the shell accounts for 1-10% of the total weight of the core-shell silicon-carbon composite material as 100%; based on the total weight of the inner core being 100%, the mass percent of the hard carbon is 50% -90%, the mass percent of the silicon-based material is 5% -40%, and the balance is amorphous carbon; wherein the silicon-based material is a mixture of silicon monoxide and silicon powder, and the mass ratio of the silicon-based material to the silicon oxide is 1:0.02-0.2, preferably 1: 0.05-0.1.
Further, in the core-shell silicon-carbon composite material, the fast ion conductor is LixNyWz, wherein X is more than or equal to 1.5 and is more than or equal to 0.5, Y is more than or equal to 3 and is more than or equal to 0.5, and N is selected from one of Ni, Co, Mn, Al, Cr, Fe, Mg, V, Zn and Cu; w is selected from SiO 4- 、SO 4 2- 、MoO 4 2- 、PO 4 3- 、TiO 3 2- And ZrO 4 3- One kind of (1). Preferably, the fast ion conductor is selected from LiNiSO 4 、LiCoMoO 4 And LiAlTiO 3 At least one of (1).
Furthermore, the ratio of the particle diameter of the silica-based material, namely the silica, to the particle diameter of the silicon powder is 1-5:1, and the particle diameter of the silica is 0.5-2 mu m.
Further, in the core-shell silicon-carbon composite material, the total weight of the core is 100%, wherein the mass percentages of the components are preferably as follows:
50to 80 percent of hard carbon
10to 20 percent of silicon-based material
10to 30 percent of amorphous carbon
The technical purpose of the second aspect of the invention is to provide a preparation method of the core-shell silicon-carbon composite material, which comprises the following steps:
preparing an inner core: dispersing silica, silicon powder and a silane coupling agent in an organic solvent, mixing, spray-drying, adding the obtained solid material into a starch aqueous solution, mixing, spray-drying, and then carbonizing in an inert atmosphere to obtain an inner core;
coating the shell: and depositing the fast ion conductor on the surface of the core by an atomic vapor deposition method to obtain the core-shell silicon-carbon composite material.
In the preparation method, when the inner core is prepared, the raw materials are added according to the following mass ratio: silicon powder: organic solvent: silane coupling agent: starch 50: (1-10): (100-500): (1-10):800-1200.
In the preparation method, the particle diameter ratio of the silica to the silicon powder is 1-5:1, and the particle diameter of the silica is 0.5-2 μm.
In the above-mentioned production method, the silane coupling agent is a sulfur-containing silane coupling agent, more specifically, the silane coupling agent is selected from the group consisting of bis (3-propyltriethoxysilane coupling agent) disulfide, bis (3-propyltriethoxysilane coupling agent) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylethoxybis (tridecylpentafluoroethyl ether) silane, 3-mercaptopropylethoxybis (propylhexapolypropylether) silane, 3-hexanoylthio-1-propyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane and 3-octanoylthio-1-propylethoxy (2-methyl-1, 3-propyleneglycol ylidene) silane.
In the above production method, the organic solvent is at least one selected from the group consisting of carbon tetrachloride, N-methylpyrrolidone, xylene and cyclohexane.
In the above production method, the starch is at least one selected from the group consisting of potato starch, corn starch, wheat starch and sweet potato starch.
In the preparation method, the carbonization is carried out for 1-6h at 800-1200 ℃ under inert atmosphere.
In the preparation method, the ball milling mode is adopted for mixing twice when the inner core is prepared.
In the above preparation method, the atomic vapor deposition method specifically includes: and vacuumizing the reaction chamber to 50-100toor, heating to the temperature of 100-300 ℃, gasifying the fast ion conductor, allowing the gasified fast ion conductor to enter the reaction chamber at a flow rate of 10-100sccm under the driving of nitrogen, adsorbing the fast ion conductor on the surface of the inner core until the air pressure of the reaction chamber reaches 5-20toor, and keeping the pressure for 1-120s to realize the coating of the fast ion conductor.
The technical purpose of the third aspect of the invention is to provide the application of the core-shell silicon-carbon composite material as a battery negative electrode material.
The embodiment of the invention has the following beneficial effects:
(1) the silicon-carbon composite material has a core-shell structure, the inner core is a composite material of hard carbon and a silicon-based material, the specific capacity of the silicon-based material is improved, and the silicon-based material is embedded into the hard carbon to reduce the expansion in the charging and discharging process; the shell is a fast ion conductor, the fast charging performance of the material is improved, the material is coated on the surface of the inner core, the defects on the surface of the inner core are reduced, and the first efficiency of the material is improved. In addition, silica-based materials, namely the silica and the nano silicon powder, are connected through a coupling agent to form a network structure, and the silica with relatively large particle size is further adopted, so that the agglomeration of the nano silicon can be reduced, the nano silicon powder has the characteristic of high electronic conductivity, and the multiplying power performance in the charging and discharging process is improved.
(2) According to the core-shell silicon-carbon composite material, starch is used as a hard carbon raw material in the preparation process of the core, porous hard carbon is formed after carbonization, and silicon-based materials are doped in hard carbon pores in the carbonization process to obtain the composite material core; and a silane coupling agent is also added in the preparation process of the core to connect carbon and silicon, so that the expansion of the material in the charge and discharge process is further reduced. The shell deposits the fast ion conductor on the surface of the hard carbon-silicon of the inner core through the atomic vapor deposition method, on one hand, the fast charging performance of the material is improved by means of the characteristic that the conductivity is high in the charging and discharging process of the fast ion conductor, on the other hand, the fast ion conductor is coated on the surface of the inner core through the atomic vapor deposition method, the defects on the surface of the inner core are greatly reduced, and the first efficiency of the material is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Wherein:
fig. 1 is an SEM image of the core-shell type silicon carbon composite material prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Core-shell silicon-carbon composites were prepared in examples 1-3:
example 1
S1, preparing an inner core:
mixing 50g of silica, 5g of nano silicon powder and 300g of N-methylpyrrolidone organic solvent, wherein the average particle size of the silica is 1000nm, the average particle size of the nano silicon powder is 200nm, adding 5g of bis (3-propyltriethoxysilane coupling agent) disulfide after uniform dispersion, carrying out ball milling and spray drying, adding the obtained material into 10000mL of 10 wt% potato starch aqueous solution, carrying out ball milling and spray drying, and then carbonizing at 800 ℃ for 3 hours under argon inert atmosphere to obtain the silicon-carbon composite material as the inner core.
S2, preparing the shell:
vacuumizing the reaction chamber to 80toor by an atomic vapor deposition method, heating to 200 ℃ and adding LiNiSO 4 Gasification, pulsed into the reaction chamber at a flow rate of 50sccm under nitrogen drive，LiNiSO 4 Adsorbing the core-shell silicon-carbon composite material on the surface of the inner core until the air pressure of the reaction chamber reaches 10toor, and keeping the air pressure for 60s to obtain the core-shell silicon-carbon composite material.
Example 2
S1, preparing an inner core:
mixing 50g of silica, 1g of nano silicon powder and 100g of carbon tetrachloride, wherein the average particle size of the silica is 500nm, the average particle size of the nano silicon powder is 100nm, adding 1g of bis (3-propyltriethoxysilane coupling agent) tetrasulfide after uniform dispersion, carrying out ball milling and spray drying, adding the obtained material into 10000mL of 10 wt% corn starch aqueous solution, carrying out ball milling and spray drying, and then carbonizing at 800 ℃ for 6 hours under argon inert atmosphere to obtain the silicon-carbon composite material as the core.
S2, preparing the shell:
by atomic vapor deposition, the reaction chamber was evacuated to 50toor, heated to 100 deg.C, and LiCoMoO was added 4 Vaporizing, pulsing into the reaction chamber at a flow rate of 10sccm under nitrogen-carrying conditions, LiCoMoO 4 Adsorbing the core-shell silicon-carbon composite material on the surface of the inner core until the air pressure of the reaction chamber reaches 5toor, and keeping the air pressure for 1s to obtain the core-shell silicon-carbon composite material.
Example 3
S1, preparing an inner core:
mixing 50g of silica, 10g of nano silicon powder and 500g of cyclohexane organic solvent, wherein the average particle size of the silica is 2000nm, the average particle size of the nano silicon powder is 500nm, adding 10g of 3-mercaptopropylethoxy di (tridecyl penta-ethyl ether) silane after uniform dispersion, carrying out ball milling and spray drying, adding the obtained material into 2000mL of 50 wt% wheat starch aqueous solution, carrying out ball milling and spray drying, and carbonizing at 800 ℃ for 6 hours under argon inert atmosphere to obtain the silicon-carbon composite material as an inner core.
S2, preparing the shell:
vacuumizing the reaction chamber to 100toor by an atomic vapor deposition method, heating to 300 ℃, and adding LiAlTiO 3 Gasifying, pulsing into the reaction chamber at a flow rate of 100sccm under nitrogen-carrying conditions, LiAlTiO 3 Adsorbing on the surface of the inner core until the gas pressure in the reaction chamber reaches 20toor, keeping for 120s, obtaining the core-shell silicon-carbon composite material.
Comparative example 1
Adding 50g of silicon monoxide into 10000mL of 10 wt% potato starch aqueous solution, carrying out ball milling and spray drying, and carbonizing at 800 ℃ for 3h under an argon inert atmosphere to obtain the silicon-carbon composite material.
Comparative example 2
Uniformly mixing 100g of corn starch and 10g of asphalt by a ball mill, heating to 200 ℃ under an inert atmosphere, polymerizing for 1h, carbonizing for 3h at 800 ℃ under the protection of inert gas, and cooling to room temperature to obtain the hard carbon composite material.
Comparative example 3
S1, preparing an inner core:
the same as S1 in example 1.
S2, bonding the shell by a solution method:
taking 100g S1 prepared core, adding 5g LiNiSO 4 10g of asphalt binder and 100mL of butanediol, uniformly mixing and stirring, filtering, transferring to a tubular furnace, carbonizing at 800 ℃ for 3h under argon atmosphere, and crushing to obtain the silicon-carbon composite material.
Comparative example 4
The procedure was carried out in the same manner as in example 1 except that 50g of silica was changed to 68.2g of silica (the weight of the silicon element added in the system was the same as that in example 1), thereby obtaining a core-shell type silicon-carbon composite material.
Comparative example 5
The procedure of example 1 was followed except that no silica was added to obtain a core-shell type silicon-carbon composite material.
Comparative example 6
The same procedure as in example 1 was repeated except that 50g of silica and 5g of silica nanoparticles were replaced with 1g of silica and 50g of silica nanoparticles to obtain a core-shell type silicon-carbon composite material.
Performance testing of the materials prepared in the above examples and comparative examples:
(1) SEM test
The core-shell silicon-carbon composite material prepared in example 1 was subjected to SEM test, and the test results are shown in fig. 1.
As can be seen from FIG. 1, the composite material prepared in example 1 has a granular structure and a relatively uniform size distribution, and the particle size is between 2 and 10 μm.
(2) Physicochemical Properties and button cell test
The composite materials prepared in examples 1 to 3 and comparative examples 1 to 6 were subjected to particle size, true density, tap density, specific surface area, ash content and specific capacity tests. The method is tested according to the method of the national standard GBT-245359-2019 graphite cathode material of the lithium ion battery. The test results are shown in table 1.
TABLE 1
The composite materials in the embodiments 1-3 and the comparative examples 1-6 are used as the negative electrode materials of the lithium ion batteries to assemble the button batteries, and the specific preparation method of the negative electrode materials comprises the following steps: adding a binder, a conductive agent and a solvent into the composite material, stirring and pulping, coating the mixture on a copper foil, and drying and rolling the copper foil to obtain the copper-clad laminate. The binder is LA132 binder, conductive agent SP, solvent is secondary distilled water, and the weight percentage of the composite material is as follows: SP: LA 132: 90g of redistilled water: 4 g: 6 g: 220mL, preparing a negative pole piece; a metal lithium sheet is used as a positive electrode; LiPF is adopted as electrolyte 6 EC + DEC, LiPF in electrolyte 6 The electrolyte is a mixture of EC and DEC with the volume ratio of 1:1 as a solvent, and the electrolyte concentration is 1.3 mol/L; the diaphragm adopts a composite film of polyethylene PE, polypropylene PP or polyethylene propylene PEP. Button cell assembly was performed in an argon-filled glove box. The electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.005V to 2.0V, the charging and discharging rate is 0.1C, the first discharging capacity and the first efficiency of the button cell are tested, and the rate performance (5C, 0.1C) and the cycle performance (0.5C/0.5C, 200 times) are tested at the same time. Test results such asShown in table 2.
TABLE 2
As can be seen from tables 1 and 2, the material prepared in the embodiment of the present invention has high specific capacity and first efficiency, because the doped silicon monoxide and silicon in the material act synergistically to increase the specific capacity of the material, and at the same time, the surface of the material is coated with the fast ion conductor to reduce the irreversible capacity loss of the material, thereby increasing the first efficiency and rate capability of the material, and the atomic vapor deposition method has the characteristic of high coating density, thereby increasing the tap density of the material. Compared with the comparative example 3, the atomic vapor deposition method has the advantages that compared with the material prepared by the traditional liquid phase coating method, the density of the material in the example 1 is high, the electronic impedance is low, the activity of the material, the specific capacity of the material and the first efficiency are improved, and the rate capability is improved.
(3) Testing the soft package battery:
the composite materials in examples 1-3 and comparative examples 1-6 were mixed and coated to prepare a negative electrode plate made of a ternary material (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) As the positive electrode, LiPF 6 (the solvent is EC + DEC, the volume ratio is 1:1, and the electrolyte concentration is 1.3mol/L) is used as electrolyte, and Celgard2400 membrane is used as a diaphragm to prepare the 1Ah flexible package battery.
And testing the rate performance of the soft package battery, wherein the charging and discharging voltage range is 2.75-4.2V, the temperature is 25 +/-3.0 ℃, the soft package battery is charged at 1.0C, 3.0C, 5.0C, 10.0C and 20.C, and the soft package battery is discharged at 1.0C. The results are shown in Table 3.
TABLE 3
As can be seen from table 3, the rate charge performance of the pouch cells prepared from the materials of examples 1-3 is significantly better than that of comparative examples 1-2, i.e., the charging time is shorter, and the analytical reason is that: in the embodiment, the surface of the negative electrode material is coated with a fast ion conductor with high lithium ion conductivity, and compared with a solid phase coating method, the atomic vapor deposition method is adopted, so that the amorphous carbon coated on the surface of the hard carbon material has the characteristics of high density and stable structure, and the rate capability is improved.
(4) And (3) testing cycle performance:
the cycle performance test conditions are as follows: the charging and discharging current is 0.5C/1C, the voltage range is 2.5-4.2V, and the cycle times are 1000 times. The test results are shown in Table 4.
TABLE 4
It can be seen from table 4 that the cycle performance of the lithium ion batteries prepared using the composites obtained in examples 1-3 is significantly better than that of the comparative examples at each stage. Experimental results show that the fast ion conductor deposited on the surface of the hard carbon by the atomic vapor deposition method has the characteristics of high density, stable structure and strong ionic conductivity, and the hard carbon expansion of the core is low in binding the expansion of silicon in the charge-discharge process, so that the cycle performance is improved.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. A core-shell silicon-carbon composite material is characterized in that the core is a composite material comprising hard carbon, amorphous carbon and silicon-based material components, and the shell is a fast ion conductor; the shell accounts for 1-10% of the total weight of the core-shell silicon-carbon composite material as 100%; based on the total weight of the inner core being 100%, the mass percent of the hard carbon is 50% -90%, the mass percent of the silicon-based material is 5% -40%, and the balance is amorphous carbon; wherein the silicon-based material is a mixture of silicon monoxide and silicon powder, and the mass ratio of the silicon-based material to the silicon oxide is 1: 0.02-0.2.
2. The core-shell silicon-carbon composite material of claim 1, wherein the fast ion conductor is LixNyWz, wherein 1.5 ≥ X ≥ 0.5, 1.5 ≥ Y ≥ 0.5, 3 ≥ Y ≥ 0.5, and N is selected from one of Ni, Co, Mn, Al, Cr, Fe, Mg, V, Zn and Cu; w is selected from SiO 4- 、SO 4 2- 、MoO 4 2- 、PO 4 3- 、TiO 3 2- And ZrO 4 3- To (3) is provided.
3. The core-shell silicon-carbon composite material according to claim 1, wherein the ratio of the particle sizes of the silica and the silicon powder is 1-5:1, and the particle size of the silica is 0.5-2 μm.
4. A method for preparing the core-shell silicon-carbon composite material according to any one of claims 1 to 3, comprising the steps of:
preparing an inner core: dispersing silica, silicon powder and a silane coupling agent in an organic solvent, mixing, spray-drying, adding the obtained solid material into a starch aqueous solution, mixing, spray-drying, and then carbonizing in an inert atmosphere to obtain an inner core;
coating the shell: and depositing the fast ion conductor on the surface of the core by an atomic vapor deposition method to obtain the core-shell silicon-carbon composite material.
5. The preparation method according to claim 4, wherein when preparing the inner core, the raw materials are added according to the following mass ratio: silicon powder: organic solvent: silane coupling agent: starch is 50:1-10: 100-.
6. The preparation method according to claim 4, wherein the particle diameter ratio of the silica to the silicon powder is 1-5:1, and the particle diameter of the silica is 0.5-2 μm.
7. The method according to claim 4, wherein the silane coupling agent is selected from the group consisting of bis (3-propyltriethoxysilane coupling agent) disulfide, bis (3-propyltriethoxysilane coupling agent) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylethoxybis (tridecylpentaethylether) silane, 3-mercaptopropylethoxybis (propylhexapolypropylether) silane, 3-hexanoylthio-1-propyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, and 3-octanoylthio-1-propylethoxy (2-methyl- 1, 3-propanediol subunit) silane.
8. The production method according to claim 4, wherein the organic solvent is at least one selected from the group consisting of carbon tetrachloride, N-methylpyrrolidone, xylene, and cyclohexane.
9. The method according to claim 4, wherein the atomic vapor deposition method is specifically: and vacuumizing the reaction chamber to 50-100toor, heating to the temperature of 100-300 ℃, gasifying the fast ion conductor, feeding the gasified fast ion conductor into the reaction chamber at a flow rate of 10-100sccm under the carrying of nitrogen, adsorbing the fast ion conductor on the surface of the inner core until the air pressure of the reaction chamber reaches 5-20toor, and keeping the pressure for 1-120s to realize the coating of the fast ion conductor.
10. Use of the core-shell silicon-carbon composite material according to claim 1 as a battery negative electrode material.
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Address after: No. 8, Jiangzhuang Road, Bieqiao Town, Liyang City, Changzhou City, Jiangsu Province, 213300 Applicant after: Changzhou enyuangu New Material Technology Co.,Ltd. Address before: 213000 No. 26, Xueye Road, Xinbei District, Changzhou City, Jiangsu Province Applicant before: Changzhou enyuangu New Material Technology Co.,Ltd. |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |