CN116387484A - Preparation method of graphene composite material, graphene composite material and application of graphene composite material - Google Patents
Preparation method of graphene composite material, graphene composite material and application of graphene composite material Download PDFInfo
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- CN116387484A CN116387484A CN202310364408.6A CN202310364408A CN116387484A CN 116387484 A CN116387484 A CN 116387484A CN 202310364408 A CN202310364408 A CN 202310364408A CN 116387484 A CN116387484 A CN 116387484A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000000741 silica gel Substances 0.000 claims abstract description 8
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 8
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000000499 gel Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 229920005591 polysilicon Polymers 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 8
- 235000002949 phytic acid Nutrition 0.000 claims description 8
- 229940068041 phytic acid Drugs 0.000 claims description 8
- 239000000467 phytic acid Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 16
- 229920000767 polyaniline Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005227 alkyl sulfonate group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- 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
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- 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 discloses a preparation method of a graphene composite material, the graphene composite material and application thereof, and the preparation method of the graphene composite material comprises the following steps: s1, mixing an aqueous solution of graphene oxide, an organic solvent dispersion liquid of silicon powder and a surfactant according to a mass ratio of 2-5:2-5:1, and adding NaBH (sodium silicate-alumina) 4 The reaction is carried out by the reduction,obtaining graphene/silica gel after hydrothermal reaction; s2, drying the graphene/silicon gel obtained in the step S1, and performing freeze drying and heat treatment to obtain a graphene/silicon compound; s3, mixing the graphene/silicon compound obtained in the step S2 with organic acid and aniline monomer according to a mass ratio of 1.5-3: mixing at a ratio of 1.5-3:1, adding an initiator to perform polymerization reaction, and drying in vacuum to obtain the final product. The graphene composite material has the advantages of good conductivity, good cycle performance, high specific capacity, good multiplying power performance and the like, and has a good application prospect in the field of lithium battery preparation.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a graphene composite material, the graphene composite material and application thereof.
Background
The lithium ion battery has the advantages of large specific capacity, high working voltage, good safety, small pollution and the like, and is widely applied to portable electronic equipment, electric automobiles and energy storage equipment in the modern society. However, as the power of the device increases, the capacity of the conventional lithium ion battery cannot meet the daily requirement, and a battery with high capacity becomes a hot spot for research. The negative electrode material is used as a storage main body of lithium ions in the charging and discharging process, and is used for controlling the intercalation and deintercalation of the lithium ions in the working process of the battery, so that the negative electrode material is a key for improving the parameters of the capacity, the cycle performance, the charging and discharging performance and the like of the lithium ion battery. The theoretical specific capacity of the current commercial anode material-graphite is 372mAh/g, so that the improvement of the battery capacity is greatly limited, and the requirement of the market on high energy density is gradually not met. Therefore, development of a novel anode material having a high specific capacity is urgent.
The theoretical capacity of the silicon material can reach 4200mAh/g, but when the silicon material is used as the negative electrode material of the lithium ion battery, the volume change is large and reaches 300% in the adsorption and desorption processes of lithium ions, so that the silicon negative electrode is cracked, the charge and discharge cycle performance is extremely poor, and the application is difficult to realize.
At present, related technologies are used for preparing composite materials from silicon and graphene and preparing high-capacity graphene anode materials, but the long-term charge and discharge performance of the graphene anode materials is still poor.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a preparation method of the graphene composite material, the graphene composite material and application thereof, and the graphene composite material has the advantages of good conductivity, good cycle performance, high specific capacity, good rate capability and the like, and has a good application prospect in the field of lithium battery preparation.
In a first aspect of the present invention, a method for preparing a graphene composite material is provided, including the steps of:
s1, mixing an aqueous solution of graphene oxide, an organic solvent dispersion liquid of silicon powder and a surfactant according to a mass ratio of 2-5:2-5:1, and adding NaBH (sodium silicate-alumina) 4 Reducing, and performing hydrothermal reaction to obtain graphene/silica gel;
s2, drying the graphene/silicon gel obtained in the step S1, and performing freeze drying and heat treatment to obtain a graphene/silicon compound;
s3, mixing the graphene/silicon compound obtained in the step S2 with organic acid and aniline monomer according to a mass ratio of 1.5-3: mixing at a ratio of 1.5-3:1, adding an initiator to perform polymerization reaction, and drying in vacuum to obtain the final product.
According to the invention, the graphene oxide is dispersed by adopting the aqueous solution, and the silicon powder is dispersed by adopting the organic solvent, so that the obtained aqueous solution of the graphene oxide and the organic solvent dispersion of the silicon powder are mixed more uniformly, and the agglomeration phenomenon is avoided. After the organic solvent is dried, graphene/silica gel with multiple pores and increased specific surface area can be formed, and after freeze drying, the structure of the graphene/silica gel is solidified, and the pores of the graphene/silica gel are further increased. The porous graphene/silicon composite prepared by the method has the advantages that the bonding strength of silicon and graphene is improved, the volume expansion of silicon in the charging and discharging process can be effectively buffered, and the cycle performance of silicon is improved. In addition, the existence of pore channels in the graphene/silicon composite can increase the reaction rate of lithium intercalation, thereby being beneficial to improving the rate capability of the composite.
According to the invention, polyaniline is further used for coating the prepared graphene/silicon composite, and in-situ coating of polyaniline can not only prevent side reaction of the graphene/silicon composite and electrolyte, but also further relieve volume expansion of silicon in the lithium intercalation and deintercalation process, so that the graphene composite material prepared by the method has good cycle performance and rate capability.
According to some embodiments of the invention, the temperature of the hydrothermal reaction is 120 ℃ to 180 ℃.
According to some embodiments of the invention, the hydrothermal reaction time is 4-10 hours.
According to some embodiments of the invention, the mass ratio of the aqueous solution of graphene oxide, the organic solvent dispersion of silicon powder and the surfactant is 3-5:2-3:1.
According to some embodiments of the invention, the graphene oxide aqueous solution has a mass fraction of 50% -80%.
According to some embodiments of the invention, the graphene oxide is prepared from modified hummers.
According to some embodiments of the invention, the modified hummers method comprises the steps of:
mixing concentrated sulfuric acid, graphite powder, potassium persulfate and phosphorus pentoxide, adding potassium permanganate, reacting for 1-4 h at 15-25 ℃, then heating to 40-50 ℃ for continuous reaction for 1-4 h, adding deionized water and hydrogen peroxide solution into the reaction system, reacting for 1-4 h at 90-100 ℃, carrying out solid-liquid separation, and vacuum drying to obtain the product.
Preferably, the mass ratio of the graphite powder to the potassium persulfate to the phosphorus pentoxide is 2-4: 1 to 1.5:1.
Preferably, the mass volume ratio of the graphite powder to the concentrated sulfuric acid is 1mg: 15-30 mL.
Preferably, the mass ratio of the potassium permanganate to the graphite powder is 1-2:1.
Preferably, the volume ratio of deionized water to concentrated sulfuric acid is 1:1.5-2.
Preferably, the volume ratio of the hydrogen peroxide solution to the concentrated sulfuric acid is 1:30-50.
Preferably, the mass concentration of the hydrogen peroxide solution is 20% -30%.
The functionalized graphene prepared by the method has higher oxidation degree, enhanced dispersion performance in aqueous solution, reduced self agglomeration phenomenon, more favorable combination with silicon powder, and contribution to forming graphene/silica gel with more uniform pores, thereby increasing the specific surface area of the graphene/silica gel.
According to some embodiments of the invention, the mass fraction of the organic solvent dispersion of the silicon powder is 40% -80%.
According to some embodiments of the invention, the organic solvent comprises at least one of ethanol, ethylene glycol, glycerol.
According to some embodiments of the invention, the silicon powder has a particle size of 200-300 nm.
The agglomeration phenomenon of the silicon powder is serious if the particle size of the silicon powder is too small; on the contrary, if the grain diameter of the silicon powder is too large, sedimentation is easy to occur, and the silicon powder cannot be uniformly dispersed in an organic solvent.
According to some embodiments of the invention, the silicon powder is Siemens-made polycrystalline silicon.
According to some embodiments of the invention, the surfactant is selected from at least one of cetyltrimethylammonium bromide, sodium secondary alkyl sulfonate, sodium fatty alcohol ether sulfate.
According to some embodiments of the invention, the NaBH 4 The mass ratio of the graphene oxide to the graphene oxide is 5-10:1.
According to some embodiments of the invention, in the step S2, the drying temperature is 50-80 ℃ and the drying time is 3-6 hours;
preferably, the freeze-drying temperature is-70 ℃ to-50 ℃ and the freeze-drying time is 24-72 hours;
preferably, the temperature of the heat treatment is 600-1000 ℃, and the time of the heat treatment is 2-6 h.
According to some embodiments of the invention, the organic acid is phytic acid.
When phytic acid is used as the acid medium, the nitrogen (i.e., amine and imine groups) on the aniline chain protonates and crosslinks it, while H + The imide group is protonated to have conductivity. Compared with an inorganic acid system, the phytic acid system has relatively higher conductivity due to relatively higher pH value and slower reaction rate, and the generated polyaniline particles are smaller.
According to some embodiments of the invention, the molar ratio of the initiator to the aniline monomer is 1-1.5:1.
According to some embodiments of the invention, the initiator is ammonium persulfate.
According to some embodiments of the invention, the polymerization reaction temperature is-4 ℃ to 4 ℃.
According to some embodiments of the invention, the polymerization time is 2 to 6 hours.
In a second aspect of the present invention, a graphene composite material is provided, and the graphene composite material is prepared by the preparation method.
In a third aspect of the present invention, a lithium ion battery is provided, in which the negative electrode includes the graphene composite material described above.
The beneficial effects are that:
according to the graphene composite material disclosed by the invention, graphene, silicon powder and a surfactant are cooperatively used to form a pore structure, and the high conductivity and the large mechanical strength of the graphene are utilized to reduce the expansion rate of the silicon material in the charge and discharge process, so that the volume change of the composite material can be effectively controlled, and the dispersion of the surfactant is promoted to prevent the agglomeration phenomenon. The graphene, the silicon powder and the surfactant are uniformly mixed by adopting a hydrothermal method, the materials have stronger binding force, and the pores of the material are increased while the material structure is maintained by adopting a freeze-drying method, so that the volume expansion of silicon can be contained, the specific surface area of the graphene composite material is improved, and the cycle performance of the material is improved.
The graphene composite material is used for a lithium ion battery cathode, is charged and discharged at 100mAh/g, and after 100 times of circulation, the specific capacity is still kept above 1350mAh/g, so that the graphene composite material is expected to be used in a large scale.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
S1, adding 40mg of graphite powder and 20mg of potassium persulfate and 20mg of phosphorus pentoxide into 0.8L of concentrated sulfuric acid, stirring for 4 hours, slowly adding 80mg of potassium permanganate powder at room temperature, keeping the temperature of the whole system at about 20 ℃ in the process, stirring for 2 hours, heating to 45 ℃, preserving heat for 2 hours, dropwise adding 0.5L of deionized water into the obtained mixed solution, controlling the temperature at 95 ℃, dropwise adding 20mL of hydrogen peroxide solution with the mass fraction of 30%, stirring for 3 hours to be uniform, centrifugally filtering, washing to be neutral by deionized water, and vacuum drying to obtain powdery graphene oxide;
s2, adding 50mg of graphene oxide into 20mL of water, and performing ultrasonic dispersion for 20min at room temperature to obtain a graphene oxide solution;
s3, adding Siemens polysilicon into 5M hydrogen fluoride solution, ultrasonically cleaning for 10min, centrifugally filtering, controlling the grain size range to be 200-300 nm, taking 50mg of Siemens polysilicon after cleaning, adding the Siemens polysilicon into a mixed solution consisting of 10mL of ethanol and 10mL of ethylene glycol, uniformly dispersing, and preparing silicon dispersion liquid;
s4, according to the mass ratio of 7:5:2 mixing graphene oxide solution, silicon powder dispersion liquid and hexadecyl trimethyl ammonium bromide, performing ultrasonic reaction for 4 hours, and then adding NaBH 4 Reduction (NaBH) 4 The mass ratio of the graphene oxide to the graphene oxide is 7.5:1), and the obtained mixed solution is placed in a reaction kettle and subjected to hydrothermal reaction at 150 ℃ for 8 hours; drying at normal pressure and 60 ℃ for 5 hours, freeze-drying at-60 ℃ for 48 hours, and finally annealing at 800 ℃ for 4 hours under argon atmosphere to obtain the porous graphene/silicon composite material;
s5, dispersing 80mg of the obtained porous graphene/silicon composite material in 100 mu L of phytic acid solution (the content is 50%, a small amount of surfactant is added according to requirements), adding 30 mu L of aniline monomer, magnetically stirring for 1h under the ice water bath condition, then dropwise adding ammonium persulfate initiator (the molar ratio of ammonium persulfate to aniline monomer is 1:1), and continuously stirring for 4h. And washing to remove the phytic acid and byproducts remained in the reaction, and vacuum drying to obtain the polyaniline-coated porous graphene/silicon composite material.
Example 2
S1, adding 40mg of graphite powder and 20mg of potassium persulfate and 20mg of phosphorus pentoxide into 0.8L of concentrated sulfuric acid, stirring for 4 hours, slowly adding 80mg of potassium permanganate powder at room temperature, keeping the temperature of the whole system at about 25 ℃ in the process, stirring for 1.5 hours, heating to 40 ℃, preserving heat for 1 hour, dropwise adding 0.5L of deionized water into the obtained mixed solution, controlling the temperature to 100 ℃, dropwise adding 20mL of hydrogen peroxide solution with the mass fraction of 30%, stirring for 3 hours to be uniform, centrifugally filtering, washing to be neutral by deionized water, and vacuum drying to obtain powdery graphene oxide;
s2, adding 50mg of graphene oxide into 25mL of water, and performing ultrasonic dispersion for 30min at room temperature to obtain a graphene oxide solution;
s3, adding Siemens polysilicon into 5M hydrogen fluoride solution, ultrasonically cleaning for 10min, centrifugally filtering, controlling the grain size range to be 200-300 nm, taking 50mg of Siemens polysilicon after cleaning, adding the Siemens polysilicon into a mixed solution composed of 15mL of propylene glycol and 10mL of ethylene glycol, uniformly dispersing, and preparing silicon dispersion liquid;
s4, according to the mass ratio of 9:4:2 mixing graphene oxide solution, silicon powder dispersion liquid and hexadecyl trimethyl ammonium bromide, performing ultrasonic reaction for 4 hours, and then adding NaBH 4 Reduction (NaBH) 4 The mass ratio of the graphene oxide to the graphene oxide is 7:1), and the obtained mixed solution is placed in a reaction kettle to be subjected to hydrothermal reaction at 180 ℃ for 6 hours; drying at normal pressure and 50 ℃ for 4 hours, freeze-drying at-60 ℃ for 72 hours, and finally annealing at high temperature of 850 ℃ for 5 hours under argon atmosphere to obtain the porous graphene/silicon composite material;
s5, dispersing 60mg of the obtained porous graphene/silicon composite material in 120 mu L of phytic acid solution (the content is 50%, a small amount of surfactant can be added according to requirements), adding 30 mu L of aniline monomer, magnetically stirring for 1h under the ice water bath condition, then dropwise adding ammonium persulfate initiator (the molar ratio of ammonium persulfate to aniline monomer is 1:1), and continuously stirring for 4h. And washing to remove the phytic acid and byproducts remained in the reaction, and vacuum drying to obtain the polyaniline-coated porous graphene/silicon composite material.
Example 3
S1, adding 50mg of graphite powder and 25mg of potassium persulfate and 20mg of phosphorus pentoxide into 0.75L of concentrated sulfuric acid, stirring for 5 hours, slowly adding 90mg of potassium permanganate powder at room temperature, keeping the temperature of the whole system at about 20 ℃ in the process, stirring for 2 hours, heating to 50 ℃, preserving heat for 1 hour, dropwise adding 0.6L of deionized water into the obtained mixed solution, controlling the temperature at 90 ℃, dropwise adding 30mL of 30% hydrogen peroxide solution, stirring for 3 hours to uniformity, centrifugally filtering, washing to be neutral by deionized water, and drying in vacuum to obtain powdery graphene oxide;
s2, adding 40mg of graphene oxide into 20mL of water, and performing ultrasonic dispersion for 20min at room temperature to obtain a graphene oxide solution;
s3, adding Siemens polysilicon into 5M hydrogen fluoride solution, ultrasonically cleaning for 15min, centrifugally filtering, controlling the grain size range to be 200-300 nm, taking 60mg of Siemens polysilicon after cleaning, adding the Siemens polysilicon into a mixed solution consisting of 10mL of propylene glycol and 20mL of ethanol, uniformly dispersing, and preparing silicon dispersion liquid;
s4, according to the mass ratio of 8:5:2 mixing graphene oxide solution, silicon powder dispersion liquid and hexadecyl trimethyl ammonium bromide, performing ultrasonic reaction for 3 hours, and then adding NaBH 4 Reduction (NaBH) 4 The mass ratio of the graphene oxide to the graphene oxide is 8.5:1), and the obtained mixed solution is placed in a reaction kettle and subjected to hydrothermal reaction for 9 hours at 160 ℃; drying at normal pressure and 55 ℃ for 3 hours, freeze-drying at-60 ℃ for 48 hours, and finally annealing at a high temperature of 800 ℃ for 6 hours under argon atmosphere to obtain the porous graphene/silicon composite material;
s5, dispersing 70mg of the obtained porous graphene/silicon composite material in 200 mu L of phytic acid solution (the content is 50%, a small amount of surfactant can be added according to requirements), adding 40 mu L of aniline monomer, magnetically stirring for 1h under the ice water bath condition, then dropwise adding ammonium persulfate initiator (the molar ratio of ammonium persulfate to aniline monomer is 1.2:1), and continuously stirring for 5h. And washing to remove the phytic acid and byproducts remained in the reaction, and vacuum drying to obtain the polyaniline-coated porous graphene/silicon composite material.
Comparative example 1
Reference to the preparation of example 1, the difference is: step S3 is not included.
Comparative example 2
Reference to the preparation of example 1, the difference is: step S5 is not included.
Comparative example 3
Reference to the preparation of example 1, the difference is: the step S5 comprises the following steps:
1g of the obtained porous graphene/silicon composite material is dispersed in 100 mu L of phytic acid solution (the content is 50%, a small amount of surfactant is added according to the requirement), 30 mu L of aniline monomer is added, magnetic stirring is carried out for 1h under the ice water bath condition, then ammonium persulfate initiator (the molar ratio of ammonium persulfate to aniline monomer is 1:1) is added dropwise, and stirring is continued for 4h. And washing to remove the phytic acid and byproducts remained in the reaction, and vacuum drying to obtain the polyaniline-coated porous graphene/silicon composite material.
Test case
The electrical property test methods of the above examples 1 to 3 and comparative examples 1 to 3 were:
placing the obtained electrode material on a copper foil to prepare a negative electrode plate, and assembling the negative electrode plate and a metal lithium plate into a 2016-type button cell, wherein electrolyte is LiPF (lithium ion battery) of 1mol/L 6 Dissolved in DMC, and the charge-discharge cycle test is carried out at room temperature and current of 100mAh/g for 100 times in the voltage range of 0.02-1.5V.
The results of the electrical property tests of examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1 below.
TABLE 1
| Specific capacity for initial discharge (mAh/g) | Retention capacity after 100 cycles (mAh/g) | |
| Example 1 | 2446 | 1848 |
| Example 2 | 2016 | 1410 |
| Example 3 | 2054 | 1362 |
| Comparative example 1 | 574 | 310 |
| Comparative example 2 | 1755 | 709 |
| Comparative example 3 | 1822 | 916 |
From the table, the graphene composite materials prepared in the embodiments 1 to 3 of the invention have high first discharge specific capacity, can effectively reserve capacity, and have good cycle performance.
Compared with example 1, comparative example 1 contains no silicon, only graphene and polyaniline, so that the specific capacity of the first discharge is slightly increased compared with that of the conventional graphite carbon negative electrode material (372 mAh/g).
Compared with example 1, comparative example 2 has no polyaniline coating layer, and the volume expansion phenomenon of silicon in the lithium deintercalation process is serious, so that the prepared graphene composite material has poor cycle performance.
Because polyaniline and graphene are easy to agglomerate, the polymerization ratio of the polyaniline to the graphene is strictly controlled, so that an ideal polyaniline-coated graphene composite structure is achieved. The addition amount of the graphene/silicon composite material in comparative example 3 is greatly increased, and the polyaniline coating effect is poor, resulting in a decrease in the electrical properties of the graphene composite material.
The embodiments of the present invention have been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The preparation method of the graphene composite material is characterized by comprising the following steps of:
s1, mixing an aqueous solution of graphene oxide, an organic solvent dispersion liquid of silicon powder and a surfactant according to a mass ratio of 2-5:2-5:1, and adding NaBH (sodium silicate-alumina) 4 Reducing, and performing hydrothermal reaction to obtain graphene/silica gel;
s2, drying the graphene/silicon gel obtained in the step S1, and performing freeze drying and heat treatment to obtain a graphene/silicon compound;
s3, mixing the graphene/silicon compound obtained in the step S2 with organic acid and aniline monomer according to a mass ratio of 1.5-3: mixing at a ratio of 1.5-3:1, adding an initiator to perform polymerization reaction, and drying in vacuum to obtain the final product.
2. The preparation method of claim 1, wherein the mass fraction of the aqueous solution of graphene oxide is 50% -80%;
preferably, the preparation method of the graphene oxide comprises the following steps:
mixing concentrated sulfuric acid, graphite powder, potassium persulfate and phosphorus pentoxide, adding potassium permanganate, reacting for 1-4 h at 15-25 ℃, then heating to 40-50 ℃ for continuous reaction for 1-4 h, adding deionized water and hydrogen peroxide solution into the reaction system, reacting for 1-4 h at 90-100 ℃, carrying out solid-liquid separation, and vacuum drying to obtain the product.
3. The preparation method of claim 1, wherein the mass fraction of the organic solvent dispersion of the silicon powder is 40% -80%;
preferably, the grain diameter of the silicon powder is 200-300 nm;
preferably, the silicon powder is Siemens polysilicon.
4. The method of claim 1, wherein the NaBH 4 The mass ratio of the graphene oxide to the graphene oxide is 5-10:1.
5. The method according to claim 1, wherein in the step S2, the freeze-drying temperature is-70 ℃ to-50 ℃;
preferably, the temperature of the heat treatment is 600 ℃ to 1000 ℃.
6. The method of claim 1, wherein the organic acid is phytic acid.
7. The method of claim 1, wherein the molar ratio of the initiator to the aniline monomer is 1 to 1.5:1, a step of;
preferably, the initiator is ammonium persulfate.
8. The method of claim 1, wherein the polymerization reaction temperature is-4 ℃ to 4 ℃;
preferably, the polymerization reaction time is 2 to 6 hours.
9. A graphene composite material, characterized in that it is prepared by the preparation method of any one of claims 1 to 8.
10. A lithium ion battery, wherein the negative electrode comprises the graphene composite material of claim 9.
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