CN113493194A - Preparation method of high-conductivity silicon-carbon composite material - Google Patents
Preparation method of high-conductivity silicon-carbon composite material Download PDFInfo
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- CN113493194A CN113493194A CN202010267697.4A CN202010267697A CN113493194A CN 113493194 A CN113493194 A CN 113493194A CN 202010267697 A CN202010267697 A CN 202010267697A CN 113493194 A CN113493194 A CN 113493194A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011863 silicon-based powder Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000000661 sodium alginate Substances 0.000 claims description 8
- 235000010413 sodium alginate Nutrition 0.000 claims description 8
- 229940005550 sodium alginate Drugs 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 229910021426 porous silicon Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- -1 polytrifluorochloroethylene, ethylene propylene Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a high-conductivity silicon-carbon composite material, which comprises the following steps: (1) dissolving a carbon source 1 in an organic solvent 1 to form a uniform solution A with the mass fraction of 4-100%, and (2) weighing a silicon source, adding the silicon source into the solution A, uniformly mixing to obtain a product B, and drying to obtain a product C.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a preparation method of a high-conductivity silicon-carbon composite material.
Background
Silicon as a lithium ion battery negative electrode material has high theoretical specific capacity, but is accompanied by huge volume effect in the process of lithium intercalation and deintercalation, so that the cycle performance of the silicon is poor. The silicon and carbon composite material prepared by compounding the silicon and the carbon has high specific capacity and excellent performanceThe uniform doping can further improve the conductivity of the composite material. At present, a general silicon-carbon composite material needs to be prepared under a high-pressure or high-temperature condition, expensive raw materials (such as nano silicon, dopamine and the like) and dangerous and uneconomical instruments (such as a chemical vapor deposition instrument, a hydrothermal kettle, a spray pyrolysis instrument and the like) are often needed, the preparation process is complex, the preparation period is long, the silicon-carbon bonding strength is low, and uniform metal doping is difficult to realize. Such as Xu et al (QUAN X, LI J Y, SUN J K, et al. Watermelon-incorporated Si/C Microspheres with high efficiency Buffer Structures for Densely reactive Lithium-Ion Battery antibodies [ J]Advanced Energy Materials,2016,7(3), using nano-silicon, glucose, PVP and sodium carboxymethyl cellulose as raw Materials, preparing silicon carbon microspheres by a complex spray pyrolysis method, and calcining at 900 ℃ in an atmosphere to obtain a Si/C composite material with a graphitized carbon layer. Chen et al (CHEN X, YING H, CHEN J, et al. preparation of graphene supported porous Si @ C tertiary composites and electrochemical properties as high capacity materials for Li-ion batteries [ J]The preparation of SiO only by hydrothermal reaction of hollow silica with GCP at 180 ℃ for 12h2@ C composite material. Jung et al (Chul Ho Jung, Jong hyun Choi, Won-Sik Kim, Seong Hyeog Hyeon-hong. A nanopore-embedded graphic carbon shell on silicon anode for high performance lithium ion batteries,2018,6,8013) respectively use expensive nano-silicon and dopamine as silicon source and carbon source, FeCl3As modifiers at dangerous N2/H2Under the protection of mixed atmosphere, the silicon carbide material is carbonized for 3 hours at the high temperature of 900 ℃ to obtain the silicon carbon material (Fe-GC @ Si) with iron doping. In conclusion, the existing silicon-carbon composite material, especially the high-conductivity silicon-carbon composite material, is usually prepared under dangerous atmosphere such as high temperature, high pressure or containing hydrogen, and has certain dangerousness, expensive raw materials, complex preparation process and long cycle time, and particularly, the preparation method of the high-conductivity silicon-carbon composite material with strong silicon-carbon structural strength and uniformly doped metal is very few.
Disclosure of Invention
The invention aims to provide high-conductivity silicon carbonThe preparation method of the composite material can prepare the high-conductivity silicon-carbon composite material with the high-conductivity graphitized carbon layer uniformly doped with metal particles by calcining at low temperature and normal pressure, the preparation process period is short, hydrogen bonds can be formed on the surfaces of the carbon layer and a silicon source, the obtained composite material has good silicon-carbon combination and stable structure, and can be used as a lithium ion battery cathode material, the volume effect of silicon is relieved, the composite material has excellent electrochemical performance, and the problem that the silicon-carbon composite material needs to be prepared at high pressure, high temperature or H2Calcining in atmosphere and other dangerous conditions, and has the problems of long period, high energy consumption, low silicon-carbon combination degree and low carbon layer conductivity.
A preparation method of a high-conductivity silicon-carbon composite material comprises the following preparation steps;
(1) dissolving a carbon source 1 in an organic solvent to form a uniform solution A with the mass fraction of 4-100%;
(2) weighing a silicon source, adding the silicon source into the solution A, uniformly mixing to obtain a product B, and drying to obtain a product C;
(3) weighing a carbon source 2, and dissolving the carbon source 2 in deionized water to form a low-fluidity uniform solution D with the mass fraction of 8-75%;
(4) adding the product C into the solution D, and uniformly mixing to obtain a solution E;
(5) adding 0.005-1mol/L of cross-linking agent aqueous solution into the colloid E, uniformly mixing and drying to obtain a product F;
(6) calcining the product F for 2-6h under the protection of protective gas, and grinding to obtain the finished product of the silicon-carbon composite material with the particle diameter of 80nm-50 mu m.
Further, in the step (1), the carbon source 1 is one or more of polymethyl methacrylate, polytrifluorochloroethylene, ethylene propylene rubber, polyvinylidene fluoride, propanol, cyclohexanone and tetrahydrofuran; the organic solvent in the step (1) is one or more of N-octane, isoprene, carbon tetrachloride and N-methylpyrrolidone.
Further, in the step (1), the carbon source 1 and/or the organic solvent is ethanol.
Further, the mass ratio of the carbon source 1 to the silicon source in the step (2) is 2:1-1:8, and the mass ratio of the carbon source 1 to the carbon source 2 in the step (3) is 2:1-1: 4.
Further, in the step (2), the silicon source is one or more of metallurgical-grade monocrystalline silicon powder, metallurgical-grade polycrystalline silicon powder, porous silicon and silicon monoxide particles, and the average diameter of the particles is 50nm-50 μm.
Further, in the step (3), the carbon source 2 is one or more of sodium carboxymethyl cellulose, styrene butadiene rubber, sodium alginate, polyacrylic acid and polyvinyl alcohol.
Further, the mixing mode in the step (2), the step (4) and the step (5) is one of mechanical stirring, ball milling or magnetic stirring, the time is 2-12h, and the rotating speed is 20-300 r/min.
Further, the drying mode in the step (2) is one of vacuum drying and forced air drying, the drying temperature is 60-120 ℃, and the drying mode in the step (5) is one of low-temperature drying and freeze drying, and the drying temperature is zero-200 ℃.
Further, in the step (5), the cross-linking agent is one or more of calcium carbonate, calcium chloride, calcium sulfate, magnesium chloride, magnesium sulfate, ferric chloride, ferric sulfate, nickel chloride, nickel sulfate and silver nitrate.
Further, the calcination temperature in the step (6) is 350-650 ℃, the protective gas is argon or nitrogen, and the gas flow rate is 50-200 ml/min.
Compared with the prior art, the invention has the beneficial effects that: the carbon source 1 is selected from one or more of polymethyl methacrylate, polytrifluorochloroethylene, ethylene propylene rubber, polyvinylidene fluoride, propanol, cyclohexanone and tetrahydrofuran, and the drying mode is vacuum drying or forced air drying, so that the dried carbon source 1 can form a product C with a mesh-shaped carbon source 1 coating layer on the silicon surface, and the product C is added into the solution D to form an oil-in-water phase protection carbon source 1 coating layer. Selecting a carbon source 2 as one or more of sodium carboxymethyl cellulose, styrene-butadiene rubber, sodium alginate, polyacrylic acid and polyvinyl alcohol, wherein a large number of carboxyl groups are arranged on molecules of the carbon source, the surface of the exposed silicon source is easy to form a hydrogen bond, silicon and carbon form strong combination, a low-fluidity solution D can fix a product C, the product C is uniformly distributed in the solution D after being uniformly mixed, after a cross-linking agent is added, the cross-linking degree of the carbon source 2 is further increased, the structural stability of the carbon source 2 is enhanced, metal particles in the cross-linking agent are uniformly distributed in the carbon source 2 by stirring, the relative positions of the carbon source 2, the metal particles, the carbon source 1 coating and the silicon source are fixed by low-temperature drying or freeze drying, and in-situ carbonization is carried out at normal pressure and low temperature to obtain the silicon-carbon composite material with double carbon layers, and the inner carbon source 1 is formed by carbonization of the carbon source coating, the outer carbon layer is obtained by carbonizing the carbon source 2 and is a graphitized carbon layer which is stable in structure, uniformly doped with metal and high in conductivity, the structure can inhibit the volume expansion of a silicon source in the lithium desorption process, the structural stability of the material is enhanced, the conductivity of the material is improved, and the electrochemical performance of the material as a lithium ion battery cathode material is improved. When the carbon source 1 is ethanol and the organic solvent 1 is also ethanol, the organic solvent has the function of cleaning and roughening the surface of the silicon source, so that the material only has an outer carbon layer, but also has excellent electrochemical performance and structural stability. The material is prepared under normal pressure and at low calcining temperature, and the preparation process is safe, low in energy consumption and suitable for industrialization.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is a scanning electron micrograph of a highly conductive silicon carbon composite prepared in example 3;
FIG. 2 is a scanning electron microscopy spectroscopy analysis chart of the highly conductive silicon carbon composite prepared in example 5;
FIG. 3 is a graph of the cycling performance of CR2032 coin cells assembled from the silicon-carbon composites prepared in comparative examples 1, 2 and 5 at a current density of 200 mA/g;
fig. 4 is an impedance diagram of the assembled CR2032 coin cell test of the silicon-carbon composite materials prepared in comparative example 1, comparative example 2 and example 5.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Dissolving 2kg of polychlorotrifluoroethylene in isoprene to form a uniform solution A with the mass fraction of 4%;
(2) weighing 1kg of porous silicon with the average diameter of 50nm, adding the porous silicon into the solution A, mechanically stirring for 2 hours at the rotating speed of 20r/min to obtain a solution B, and carrying out forced air drying at 60 ℃ to obtain a product C;
(3) dissolving 1kg of polyacrylic acid in deionized water to form a low-fluidity uniform solution D with the mass fraction of 8%;
(4) adding the product C into the solution D, mechanically stirring for 2 hours at the rotating speed of 20r/min, and uniformly mixing to obtain a product E;
(5) adding 0.005mol/L nickel sulfate aqueous solution into the product E, mechanically stirring for 2 hours at the rotating speed of 20r/min, uniformly mixing, and drying at a low temperature of zero to obtain a product F;
(6) and calcining the product F at 350 ℃ for 2h under the protection of argon, and grinding the product F at the flow rate of 50ml/min to obtain a silicon-carbon composite material finished product with the particle diameter of 80 nm.
Example 2
(1) Dissolving 50kg of ethylene propylene rubber in N-methyl pyrrolidone to form a uniform solution A with the mass fraction of 7%;
(2) weighing 70kg of porous silicon with the average diameter of 60nm, adding the porous silicon into the solution A, mechanically stirring for 4 hours at the rotating speed of 60r/min to obtain a solution B, and carrying out forced air drying at 100 ℃ to obtain a product C;
(3) dissolving 60kg of polyvinyl alcohol in deionized water to form a low-fluidity uniform solution D with the mass fraction of 17%;
(4) adding the product C into the solution D, mechanically stirring for 5 hours at the rotating speed of 80r/min, uniformly mixing, and drying at a low temperature of zero to obtain a product E;
(5) adding 0.08mol/L silver nitrate aqueous solution into the product E, mechanically stirring for 2 hours at the rotating speed of 70r/min, uniformly mixing, and drying at a low temperature of zero to obtain a product F;
(6) and calcining the product E at 550 ℃ for 3h under the protection of nitrogen, wherein the flow rate of argon gas is 70ml/min, and grinding to obtain a finished silicon-carbon composite material with the particle diameter of 500 nm.
Example 3
(1) Dissolving 1kg of tetrahydrofuran in n-octane to form a uniform solution A with the mass fraction of 10%;
(2) weighing 4kg of silicon monoxide particles with the average diameter of 2 mu m, adding the silicon monoxide particles into the solution A, magnetically stirring the solution A for 4 hours at the rotating speed of 80r/min to obtain a solution B, and drying the solution B in vacuum at the temperature of 120 ℃ to obtain a product C;
(3) dissolving 2kg of sodium alginate in deionized water to form a low-fluidity uniform solution D with the mass fraction of 22%;
(4) adding the product C into the solution D, ball-milling for 2 hours at the rotating speed of 120r/min, and uniformly mixing to obtain a product E;
(5) adding 0.1mol/L magnesium chloride aqueous solution into the product E, mechanically stirring for 5 hours at the rotating speed of 100r/min, uniformly mixing, and drying at zero-temperature low temperature to obtain a product F;
(6) and calcining the product F for 4 hours at 480 ℃ under the protection of argon, and grinding the product F at the flow rate of 80ml/min to obtain a finished silicon-carbon composite material with the particle diameter of 2.1 mu m.
Example 4
(1) Dissolving 1kg of ethylene propylene rubber in polyvinylidene fluoride to form a uniform solution A with the mass fraction of 51%;
(2) weighing 7kg of metallurgical-grade silicon powder with the average diameter of 180nm, adding the metallurgical-grade silicon powder into the solution A, carrying out ball milling and mixing for 6 hours at the rotating speed of 110r/min to obtain a solution B, and carrying out forced air drying at 90 ℃ to obtain a product C;
(3) dissolving 4kg of polyvinyl alcohol in deionized water to form a low-fluidity uniform solution D with the mass fraction of 25%;
(4) adding the product C into the solution D, magnetically stirring for 6 hours at the rotating speed of 120r/min, and uniformly mixing to obtain a product E;
(5) adding 0.2mol/L magnesium sulfate aqueous solution into the product E, mechanically stirring for 6 hours at the rotating speed of 75r/min, uniformly mixing, and drying at a low temperature of zero to obtain a product F;
(6) and calcining the product F for 4 hours at 450 ℃ under the protection of argon, and grinding the product F at the flow rate of 80ml/min to obtain a silicon-carbon composite material finished product with the particle diameter of 200 nm.
Example 5
(1) Dissolving 1kg of polyethanol in ethanol to form a uniform solution A with the mass fraction of 100%;
(2) weighing 8kg of metallurgical-grade silicon powder with the average diameter of 50 microns, adding the metallurgical-grade silicon powder into the solution A, mechanically stirring for 12 hours at the rotating speed of 300r/min to obtain a solution B, and carrying out forced air drying at 120 ℃ to obtain a product C;
(3) dissolving 4kg of sodium alginate in deionized water to form a low-fluidity uniform solution D with the mass fraction of 60%;
(4) adding the product C into the solution D, mechanically stirring for 6 hours at the rotating speed of 300r/min, and uniformly mixing to obtain a product E;
(5) adding 1mol/L magnesium chloride aqueous solution into the product E, mechanically stirring for 12h at the rotating speed of 300r/min, uniformly mixing, and freeze-drying at the temperature of 200 ℃ below zero to obtain a product F;
(6) and calcining the product F for 6 hours at 650 ℃ under the protection of argon, wherein the flow rate of the argon is 200ml/min, and grinding to obtain a silicon-carbon composite material finished product with the particle diameter of 50 microns.
Comparative example 1
(1) Adding 3g of metallurgical-grade silicon powder with the average particle diameter of 50 mu m into 100ml of distilled water, and performing ultrasonic dispersion to form a solution A;
(2) adding 3g of polyvinylpyrrolidone (PVP), 3g of glucose and 0.5g of carboxymethyl cellulose into the solution A, and mechanically stirring for 2 hours at the rotating speed of 60r/min to form a solution B;
(3) adding 20g of flake graphite into the solution B, mechanically stirring for 2 hours at the rotating speed of 120r/min, then ball-milling for 2 hours at the rotating speed of 120r/min, and then spray-drying to obtain a product D;
(4) and placing the D under the protection of argon gas and calcining at 900 ℃ for 12h to obtain a product E with the average diameter of 50 mu m.
In the comparative example 2, the following examples were conducted,
(1) dissolving 4kg of Sodium Alginate (SA) in deionized water to form a low-fluidity uniform solution A with the mass fraction of 60%;
(2) adding 8kg of metallurgical-grade silicon powder with the average diameter of 50 microns into the solution A, mechanically stirring for 12 hours at the rotating speed of 300r/min to obtain a solution B, and freeze-drying at the temperature of 200 ℃ below zero to obtain a product C;
(3) and calcining the product C for 2 hours at 650 ℃ under the protection of argon at the flow rate of 200ml/min, and grinding to obtain a silicon-carbon composite material finished product with the particle diameter of 50 microns.
Comparative examples 1, 2 and 5 were tested using the following methods:
mixing the materials prepared in comparative examples 1, 2 and 5 as a negative electrode material with a binder polyacrylic acid (PAA) and a conductive agent (Super-P) according to a mass ratio of 80:10:10, adding a proper amount of deionized water as a solvent to prepare slurry, coating the slurry on a copper foil, and preparing a negative electrode sheet through vacuum drying and rolling; a metallic lithium plate is used as a counter electrode, and 1mol/L LiPF is used6The three-component mixed solvent is prepared by adopting a polypropylene microporous membrane as a diaphragm and assembling a CR2032 type button cell in a glove box filled with inert gas according to an electrolyte mixed by EC, DMC and EMC 1:1:1 (V/V). The charge and discharge test of the button cell is carried out on a Lanhe cell test system of blue-electron electronic corporation, Wuhan, under the conditions of room temperature and current of 200mA/g, constant-current charge and discharge are carried out, the charge and discharge voltage is limited to 0.005-2.5V, and impedance is tested by adopting a CHI600E electrochemical workstation of Shanghai Hua instruments, Inc.
Comparative example 1 or comparative example 2 is described in actual production or literature. In comparative example 1, spray drying is required in the preparation process, the requirement of instruments is high, the calcination temperature is 900 ℃, the temperature is high and dangerous, and the calcination time is 12 hours, so that the energy consumption is high, in a next step, glucose, polyvinylpyrrolidone (PVP) and flake graphite are difficult to form chemical bonding with silicon, the silicon and carbon bonding of the prepared composite material is unstable, and the carbon layer is low in conductivity without metal ion doping. In comparison with examples 1-5, only sodium alginate (one of carbon sources 2) is used as a carbon source, and no carbon source 1 and a cross-linking agent are used, the carbon layer in the prepared silicon source composite material is not doped with metal ions, the conductivity is low, which is not beneficial to the high-rate charge and discharge of the material, fig. 1 clearly shows that the surface of the high-conductivity silicon-carbon composite material prepared in example 3 has a complete carbon layer, and fig. 2 clearly shows that the metal ions of the high-conductivity silicon-carbon composite material prepared in example 5 are uniformly distributed in the material. Fig. 3 and 4 show that the performance of the highly conductive silicon-carbon composite material prepared in example 5 is far better than that of the silicon-carbon composite materials of comparative examples 1 and 2, and the preparation method of the highly conductive silicon-carbon composite material provided by the patent has the advantages of short period, green and non-toxic carbon source 2 and low calcination temperature.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a high-conductivity silicon-carbon composite material is characterized by comprising the following steps: the preparation steps comprise:
(1) dissolving a carbon source 1 in an organic solvent to form a uniform solution A with the mass fraction of 4-100%;
(2) weighing a silicon source, adding the silicon source into the solution A, uniformly mixing to obtain a product B, and drying to obtain a product C;
(3) weighing a carbon source 2, and dissolving the carbon source 2 in deionized water to form a low-fluidity uniform solution D with the mass fraction of 8-75%;
(4) adding the product C into the solution D, and uniformly mixing to obtain a solution E;
(5) adding 0.005-1mol/L of cross-linking agent aqueous solution into the colloid E, uniformly mixing and drying to obtain a product F;
(6) calcining the product F for 2-6h under the protection of protective gas, and grinding to obtain the finished product of the silicon-carbon composite material with the particle diameter of 80nm-50 mu m.
2. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: in the step (1), the carbon source 1 is one or more of polymethyl methacrylate, polytrifluorochloroethylene, ethylene propylene rubber, polyvinylidene fluoride, propanol, cyclohexanone and tetrahydrofuran; the organic solvent in the step (1) is one or more of N-octane, isoprene, carbon tetrachloride and N-methylpyrrolidone.
3. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: the carbon source 1 and/or the organic solvent in the step (1) is ethanol.
4. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: the mass ratio of the carbon source 1 to the silicon source in the step (2) is 2:1-1:8, and the mass ratio of the carbon source 1 to the carbon source 2 in the step (3) is 2:1-1: 4.
5. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: in the step (2), the silicon source is one or more of metallurgical-grade monocrystalline silicon powder, metallurgical-grade polycrystalline silicon powder, porous silicon and silicon monoxide particles, and the average diameter of the particles is 50nm-50 μm.
6. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: in the step (3), the carbon source 2 is one or more of sodium carboxymethyl cellulose, styrene butadiene rubber, sodium alginate, polyacrylic acid and polyvinyl alcohol.
7. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: the mixing mode in the step (2), the step (4) and the step (5) is one of mechanical stirring, ball milling or magnetic stirring, the time is 2-12h, and the rotating speed is 20-300 r/min.
8. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: the drying mode in the step (2) is one of vacuum drying and forced air drying, the drying temperature is 60-120 ℃, the drying mode in the step (5) is one of low-temperature drying and freeze drying, and the drying temperature is zero-200 ℃.
9. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: and (3) the cross-linking agent in the step (5) is one or more of calcium carbonate, calcium chloride, calcium sulfate, magnesium chloride, magnesium sulfate, ferric chloride, ferric sulfate, nickel chloride, nickel sulfate and silver nitrate.
10. The method for preparing the highly conductive silicon-carbon composite material according to claim 1, wherein the method comprises the following steps: the calcination temperature in the step (6) is 350-650 ℃, the protective gas is argon or nitrogen, and the gas flow rate is 50-200 ml/min.
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