CN114171717B - Silicon alkene composite material for lithium ion battery and preparation method thereof - Google Patents
Silicon alkene composite material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN114171717B CN114171717B CN202111533093.0A CN202111533093A CN114171717B CN 114171717 B CN114171717 B CN 114171717B CN 202111533093 A CN202111533093 A CN 202111533093A CN 114171717 B CN114171717 B CN 114171717B
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- silylene
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- lithium ion
- carbon nitride
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 10
- 239000010703 silicon Substances 0.000 title claims abstract description 10
- -1 Silicon alkene Chemical class 0.000 title claims description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000007833 carbon precursor Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- VTNYPPRJIKMDPS-UHFFFAOYSA-N azanium 2-dodecylpyridine chloride Chemical class [Cl-].[NH4+].C(CCCCCCCCCCC)C1=NC=CC=C1 VTNYPPRJIKMDPS-UHFFFAOYSA-N 0.000 claims description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- RZHBMYQXKIDANM-UHFFFAOYSA-N dioctyl butanedioate;sodium Chemical compound [Na].CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC RZHBMYQXKIDANM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical group CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002717 polyvinylpyridine Chemical class 0.000 claims description 2
- 239000002296 pyrolytic carbon Substances 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 2
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000004005 microsphere Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000000707 layer-by-layer assembly Methods 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000006138 lithiation reaction Methods 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- 238000010000 carbonizing Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Abstract
The invention relates to a composite microsphere based on two-dimensional nano-silicon alkene sheet, graphitized carbon nitride and coated carbon material and a preparation method thereof, wherein the material is of a pomegranate-like core-shell structure with a diameter of 5-20 microns and is mainly applied to the field of lithium ion battery cathodes. The preparation method comprises the following steps: 1) Calcining the carbon-nitrogen-containing organic material in alkali liquor after hydrothermal reaction to obtain lithiated graphite-phase carbon nitride; 2) Uniformly and tightly compounding the silylene nano-sheet and graphite phase carbon nitride in a solvent environment through an electrostatic self-assembly process; 3) Adding a carbon precursor, coating, and calcining at high temperature to form the product. The composite microsphere prepared by the preparation method disclosed by the invention benefits from the unique structure and the price bond form of the silylene nanosheets, fundamentally overcomes the defect of excessively high expansion rate of the silicon-based anode material, fully utilizes the synergistic effect of silylene and graphite phase carbon nitride, ensures that the novel anode material has the advantages of high specific capacity, long cycle life and the like, and is simple in preparation process, low in cost and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of nano materials and chemical power supplies, and particularly relates to a silylene composite material applied to the field of lithium ion battery anode materials and a preparation method thereof.
Background
The novel lithium ion secondary battery is one of hot spots developed in the field of new energy, and has become the most important power source of electric automobiles. The negative electrode material is used as one of four main raw materials of the lithium battery, and plays a very important role in the performance and safety of the lithium battery. At present, most commercial lithium ion batteries adopt graphite cathodes, the specific capacity of the graphite cathodes reaches more than 360mA/g, the specific capacity is close to the theoretical specific capacity (372 mAh/g), and the future development requirements of the lithium ion batteries cannot be met.
The silicon-based material is regarded as the negative electrode material of the next generation of high-energy-density lithium ion battery with the advantages of superhigh gram capacity (4200 mAh/g), environmental friendliness, rich reserve and the like. However, when the lithium ion battery is charged or discharged, huge volume change exists, so that the cycle performance is poor, and serious morphological change of the material is caused, so that the cycle performance of the electrode material is influenced, and the application of the lithium ion battery is limited.
To solve this problem, researchers have mostly adopted a method of alleviating expansion during lithiation by nanocrystallizing a silicon-based material or compounding with other materials. Patent document CN109301215a discloses a high-capacity silicon-carbon negative electrode active material and a preparation method thereof, wherein the porous microspherical silicon-carbon material is prepared from nano silicon, crystalline flake graphite, carbon nano tube and carbon source through ball milling, spray drying and heat treatment processes. Although the method effectively improves the cycling stability of the silicon-based negative electrode, the expansion effect of the pole piece is still obvious in the charging process, and meanwhile, the porous structure of the pole piece leads to high specific surface area of the material, more side reactions with electrolyte, low volume energy density and poor mechanical strength, and is easy to pulverize in the electrode preparation rolling process.
Although the problems of volume expansion and lower conductivity of the silicon material in the lithiation process are relieved to a certain extent by a nanocrystallization or other material compounding method, the expansion effect in the lithiation process is still obvious, and the requirements of commercial application cannot be met.
Disclosure of Invention
The invention aims at solving the problem of overhigh volume expansion rate of a silicon-based negative electrode of a lithium ion battery, and provides a silicon-alkene composite material suitable for the lithium ion battery and a preparation method thereof. The preparation method has simple process and low production cost, and is suitable for industrial production.
A novel negative electrode composite material of a lithium ion battery is characterized in that: the composite material is of a pomegranate-like core-shell structure and mainly comprises an inner core silicon alkene nano sheet and lithiated graphite phase carbon nitride in a composite mode, and an outer layer is made of a coated pyrolytic carbon material. The particle diameter D50 of the composite material is 5-20 micrometers, wherein the mass fraction of the composite material is 10-60%, the mass fraction of the composite material is 5-30%, and the mass fraction of the carbon coating material is 40-90%.
The invention also discloses a preparation method of the graphene nano sheet, the lithiated graphitized carbon nitride sheet and the carbon material composite material, which comprises the following steps:
s1: dispersing a graphite-phase carbon nitride precursor in alkali liquor containing lithium, and performing solvothermal reaction and high-temperature calcination to obtain a lithiated high-specific-surface-area graphite-phase carbon nitride sheet;
s2: dispersing the ultrasonic wave of the graphite phase carbon nitride synthesized in the step S1 in a solvent containing an anionic surfactant, dispersing the silylene nano-sheet in the solvent containing a cationic surfactant according to a required metering ratio, mixing the slurry and stirring;
s3: adding the slurry obtained in the step S2 into a carbon precursor to coat, drying, and calcining at a high temperature to form;
s4: and (3) crushing and screening the materials in the step (S3) to obtain the composite material with the pomegranate-like structure.
Specifically, in the step S1, the graphite-phase carbon nitride precursor is one or a combination of melamine, dicyandiamide, nitrile amine and urea, and the lithium source is one or a combination of lithium hydroxide, lithium carbonate, lithium chloride and lithium oxalate.
Specifically, in the step S1, the reaction temperature of the solution heat is 100-240 ℃, the reaction time is 3-36 h, the high-temperature calcination temperature is 300-800 ℃, the used atmosphere is one or a combination of air, nitrogen and argon, and the calcination time is 3-12 h.
Specifically, the anionic surfactant in step S2 is one or a combination of sodium stearate, calcium stearate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium stearyl sulfate, sodium dioctyl succinate sulfonate and sodium dodecyl benzene sulfonate. The cationic surfactant is one or a combination of polydiallyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, octadecyl phosphate substituted amine, dodecyl pyridine ammonium chloride and polyvinyl pyridine quaternary ammonium salt. The solvent is one or the combination of deionized water, methanol, ethanol and glycol.
The carbon precursor in the specific step S3 is any one or combination of asphalt, phenolic resin, chitosan, polyvinylpyrrolidone, starch, cyclodextrin and polyimide. The calcination temperature is 200-1000 ℃ and the calcination time is 3-12 h. The atmosphere is one or a combination of nitrogen, argon and hydrogen.
Specifically, the drying mode in the step S3 is one or a combination of stirring drying, spray drying and freeze drying.
The beneficial effects of the invention are as follows:
the invention provides a composite negative electrode material for a lithium ion battery and a preparation method thereof, wherein a microsphere core material is prepared by compositing a silylene nano sheet and a lithiated graphitized carbon nitride sheet by a simple and easy method, and carbon coating is carried out on the basis, so that the composite negative electrode material with a pomegranate-like structure is prepared, the problem of pole piece expansion is fundamentally solved, the long cycle life and high charge-discharge multiplying power are considered, and meanwhile, the process is simple, the production cost is low, and the preparation method is suitable for industrial production.
Furthermore, the invention replaces the traditional silicon-based material with the silicon alkene nano-sheet as the active component of the lithium ion battery cathode material, has no crystalline state change in the lithiation process, avoids the problem of anisotropic expansion of the traditional silicon source, has the expansion rate far lower than that of the traditional silicon material under complete lithiation, fully utilizes the lamellar structure and the special valence bond form on the basis, improves the intrinsic conductivity and the ion migration rate, and fundamentally ensures the excellent electrochemical performance of the composite material.
Furthermore, a large number of pi conjugated planes and nitrogen atom double bonds exist in the lithiated graphite phase carbon nitride, which is favorable for improving the stability of the silylene nanosheet, and promotes the migration rate of lithium ions and electrons by means of electron-hole pairs and vacancy defects, thereby improving the rate capability of the composite microsphere.
Furthermore, the principle of like charges repellent is adopted in a solvent environment, so that the defect that the silylene nanosheets are easy to agglomerate can be overcome, the silylene nanosheets are uniformly and tightly compounded with the graphite-phase carbon nitride matrix with different charges, and meanwhile, the phenomenon of electrochemical agglomeration in the charge-discharge process is effectively avoided by coating the surfactant.
Furthermore, the core-shell structure is formed by carbon cladding, and an expansion space is reserved, so that pulverization of the material in the circulation process is avoided, the specific surface area of the material is reduced, and side reactions of the core material and electrolyte are avoided. Helping to form a stable electrolyte solid electrolyte interfacial film.
In summary, compared with the prior art, the invention has the following beneficial effects: the high specific capacity lithium ion battery anode material prepared by the preparation method has the advantages of low expansion rate, long cycle life, good multiplying power performance, simple preparation process, low cost, energy conservation, consumption reduction and excellent performance, and is suitable for industrial production.
Drawings
The description of all figures and reference numerals in the figures referred to in the patent application are as follows:
FIG. 1 is a schematic view of a composite material structure in example 1 of the present invention;
FIG. 2 shows the result of the scanning electron microscope test of the composite material in example 1 of the present invention;
table 1 shows the results of the electrochemical performance test of the composite materials of examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. The following detailed description of embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
Example 1
Preparation of high-performance composite anode material
(1) Into a beaker was charged 8g of melamine, 1.25g of LiOH H 2 Stirring O and 60g of deionized water for 1h, transferring to a stainless steel autoclave with a tetrafluoroethylene lining, reacting for 24h at 160 ℃, washing the product with deionized water for 5 times, and calcining at 550 ℃ under nitrogen to obtain lithiated graphitized carbon nitride;
(2) Taking 0.6g of graphitized carbon nitride and 0.1g of sodium stearate in the step 1, adding 20ml of mixed solvent of ethanol and water (mass ratio of 5:1), stirring for 1h, and then performing ultrasonic dispersion for 1h;
(3) Adding 0.8g of silylene nano-sheet and 0.1g of polydiallyl dimethyl ammonium chloride into 20ml of mixed solvent of ethanol and water (mass ratio is 5:1), performing ultrasonic treatment for 1h, slowly adding the slurry in the step 2, and stirring;
(4) Adding 1.2g of chitosan into the slurry obtained in the step 3, stirring for 30min, and then spray-drying to obtain a cathode material precursor;
(5) Calcining and carbonizing the product in the step 4 at 700 ℃ for 5 hours under the protection of nitrogen;
(6) And 5, crushing and screening the materials in the step 5 to obtain the novel cathode material with the core-shell structure.
Characterization of physicochemical properties of the composite anode material:
the micro-morphology of the microsphere material obtained under the conditions is shown in figure 1, and the microsphere material can be seen to be in a better spherical structure, so that the composite material with the pomegranate-like core-shell structure is formed.
The composite material, the conductive agent and the adhesive are mixed according to the mass ratio of 80:10:10, grinding the mixture into slurry, uniformly mixing the slurry and uniformly coating the slurry on copper foil to prepare the pole piece. The pole piece is dried for 12 hours in a vacuum drying oven at 75 ℃ and then cut into a circular piece with the diameter of 1.5cm for standby. And taking the cut pole piece with the size as an anode, and taking the metal lithium piece as a cathode, and assembling the CR2032 button cell. The charge and discharge cut-off voltages are respectively 1.5V and 0.01V, and the cycle stability test is carried out under the charge and discharge conditions of 100 mAh/g. The specific capacity, first efficiency, capacity retention, and pole piece expansion rate results at full charge are shown in table 1.
Example 2
(1) Adding 8g of dicyandiamide, 1.25g of lithium carbonate and 60g of deionized water into a beaker, stirring for 1h, transferring into a stainless steel autoclave with a tetrafluoroethylene lining, reacting for 24h at 160 ℃, washing the product with deionized water for 5 times, and calcining at 550 ℃ in air to obtain lithiated graphitized carbon nitride;
(2) Taking 0.6g of lithiated graphitized carbon nitride in the step 1, adding 0.1g of sodium stearate into a mixed solvent of 20ml of ethanol and water (mass ratio of 5:1), stirring for 1h, and then performing ultrasonic dispersion for 1h;
(3) Adding 0.8g of silylene nano-sheet and 0.1g of cetyltrimethylammonium bromide into 20ml of mixed solvent of ethanol and water (mass ratio of 5:1), carrying out ultrasonic treatment for 1h, slowly adding into the slurry obtained in the step 2, and stirring;
(4) Adding 0.8g of phenolic resin into the slurry obtained in the step 3, stirring for 30min, and then stirring and drying at 75 ℃ to obtain a cathode material precursor;
(5) Calcining and carbonizing the product in the step 4 at 700 ℃ for 5 hours under the protection of nitrogen;
(6) And 5, crushing and screening the materials in the step 5 to obtain the novel cathode material with the core-shell structure.
Electrochemical test method example 1 was identical and the test results are shown in table 1.
Example 3
(1) Into a beaker was charged 8g of melamine, 1.25g of LiOH H 2 Stirring O and 60g of deionized water for 1h, transferring to a stainless steel autoclave with a tetrafluoroethylene lining, reacting for 24h at 160 ℃, washing the product with deionized water for 5 times, and calcining at 550 ℃ under nitrogen to obtain lithiated graphitized carbon nitride;
(2) Adding 0.6g of lithiated graphitized carbon nitride and 0.1g of sodium dodecyl benzene sulfonate in 20ml of ethanol in the step 1, stirring for 1h, and then performing ultrasonic dispersion for 1h;
(3) Adding 0.8g of silylene nano-sheet and 0.1g of polydiallyl dimethyl ammonium chloride into 20ml of ethanol, performing ultrasonic treatment for 1h, slowly adding the slurry obtained in the step 2, and stirring;
(4) Adding 0.8g of polyvinylpyrrolidone into the slurry obtained in the step 3, stirring for 30min, and then spray-drying to obtain a cathode material precursor;
(5) Calcining and carbonizing the product in the step 4 at 700 ℃ for 5 hours under the protection of nitrogen;
(6) And 5, crushing and screening the materials in the step 5 to obtain the novel cathode material with the core-shell structure.
Electrochemical test method example 1 was identical and the test results are shown in table 1.
Comparative example 1
(1) Into a beaker was charged 8g of melamine, 1.25g of LiOH H 2 O and 60g of deionized waterStirring the sub-water for 1h, transferring the mixture into a stainless steel autoclave lined with tetrafluoroethylene, reacting for 24h at 160 ℃, washing the product with deionized water for 5 times, and calcining the product at 550 ℃ under nitrogen to obtain lithiated graphitized carbon nitride;
(2) Taking 0.6g of graphitized carbon nitride and 0.1g of sodium stearate in the step 1, adding 20ml of mixed solvent of ethanol and water (mass ratio of 5:1), stirring for 1h, and then performing ultrasonic dispersion for 1h;
(3) Adding 0.8g of nano silicon with the particle size of 80nm and 0.1g of polydiallyl dimethyl ammonium chloride into 20ml of mixed solvent of ethanol and water (mass ratio of 5:1), carrying out ultrasonic treatment for 1h, slowly adding the slurry in the step 2, and stirring;
(4) Adding 1.2g of chitosan into the slurry obtained in the step 3, stirring for 30min, and then spray-drying to obtain a cathode material precursor;
(5) Calcining and carbonizing the product in the step 4 at 700 ℃ for 5 hours under the protection of nitrogen;
(6) And 5, crushing and screening the materials in the step 5 to obtain the novel cathode material with the core-shell structure.
Electrochemical test method example 1 was identical and the test results are shown in table 1.
Table 1 summary of electrochemical properties of the composites of examples and comparative examples
From the data in the table, the lithium ion battery anode material provided by the embodiment of the invention benefits from the unique structure of the silylene nanosheets and the reasonable micro-nano composite design of the microspheres, and has the advantages of high reversible specific capacity, high first efficiency, good cycling stability and low expansion rate of the pole pieces in the full-charge state. The preparation method fully embodies that the silylene composite material prepared by the preparation method has huge application potential.
Claims (7)
1. A silylene composite material for lithium ion batteries is characterized in that: the composite material is of a pomegranate-like core-shell structure and mainly comprises an inner core silicon alkene nano sheet and lithiated graphite phase carbon nitride in a composite mode, and an outer layer is made of a coated pyrolytic carbon material.
2. The silylene composite material for lithium ion batteries according to claim 1, wherein: the particle diameter D50 is 5-20 micrometers, wherein the silicon alkene nano sheet is 3-10 layers, the weight percentage of the composite material is 10-60%, the weight percentage of graphite phase carbon nitride is 5-30%, and the weight percentage of the carbon coating material is 40-90%.
3. The preparation method of the silylene composite material for the lithium ion battery is characterized by comprising the following steps of:
1) Dispersing a graphite-phase carbon nitride precursor in alkali liquor containing lithium, and performing solvothermal reaction and high-temperature calcination to obtain a lithiated high-specific-surface-area graphite-phase carbon nitride sheet;
2) Dispersing the ultrasonic of the graphite-phase carbon nitride synthesized in the step 1) in a solvent containing an anionic surfactant to prepare slurry, dispersing the silylene nano-sheets in the solvent containing the cationic surfactant according to a required metering ratio to prepare slurry, mixing the slurry and stirring;
3) And (3) adding the carbon precursor into the slurry obtained in the step (2) to coat, drying, calcining at high temperature to form, crushing and screening to obtain the composite material with the pomegranate-like structure.
4. The method for preparing a silylene composite material for lithium ion batteries according to claim 3, wherein the method comprises the following steps: the graphite-phase carbon nitride precursor in the step 1) is one or a combination of melamine, dicyandiamide, nitrile amine and urea, and the lithium source is one or a combination of lithium hydroxide, lithium carbonate, lithium chloride and lithium oxalate; the reaction temperature of the dissolution heat is 100-240 ℃, the reaction time is 3-36 h, the high-temperature calcination temperature is 300-800 ℃, the used atmosphere is one or the combination of air, nitrogen and argon, and the calcination time is 3-12 h.
5. The method for preparing a silylene composite material for lithium ion batteries according to claim 3, wherein the method comprises the following steps: the anionic surfactant in the step 2) is one or a combination of sodium stearate, calcium stearate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dioctyl succinate sulfonate and sodium dodecyl benzene sulfonate; the cationic surfactant is one or a combination of polydiallyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, octadecyl phosphate substituted amine, dodecyl pyridine ammonium chloride and polyvinyl pyridine quaternary ammonium salt; the solvent is one or the combination of deionized water, methanol, ethanol and glycol.
6. The method for preparing a silylene composite material for lithium ion batteries according to claim 3, wherein the method comprises the following steps: the carbon precursor in the step 3) is any one or combination of asphalt, phenolic resin, chitosan, polyvinylpyrrolidone, starch, cyclodextrin and polyimide; the calcination temperature is 200-1000 ℃, the calcination time is 3-12 h, and the atmosphere is one or the combination of nitrogen, argon and hydrogen.
7. The method for preparing a silylene composite material for lithium ion batteries according to claim 3, wherein the method comprises the following steps: the drying mode in the step 3) is one or a combination of stirring drying, spray drying and freeze drying.
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