CN115092905A - Amorphous carbon material modified by carbon points and preparation method and application thereof - Google Patents
Amorphous carbon material modified by carbon points and preparation method and application thereof Download PDFInfo
- Publication number
- CN115092905A CN115092905A CN202210872316.4A CN202210872316A CN115092905A CN 115092905 A CN115092905 A CN 115092905A CN 202210872316 A CN202210872316 A CN 202210872316A CN 115092905 A CN115092905 A CN 115092905A
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- Prior art keywords
- carbon
- amorphous carbon
- treatment
- carbon source
- amorphous
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Links
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 136
- 239000002194 amorphous carbon material Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 81
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- 238000000034 method Methods 0.000 claims abstract description 18
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- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 53
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 239000011295 pitch Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 20
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- 238000001035 drying Methods 0.000 claims description 10
- 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 claims description 9
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- 238000010306 acid treatment Methods 0.000 claims description 6
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 6
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
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- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
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- 229910052751 metal Inorganic materials 0.000 claims description 2
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- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- OSNSWKAZFASRNG-WNFIKIDCSA-N (2s,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol;hydrate Chemical compound O.OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O OSNSWKAZFASRNG-WNFIKIDCSA-N 0.000 claims 1
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- 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 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
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- 238000001354 calcination Methods 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 229910021384 soft carbon Inorganic materials 0.000 description 25
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- 238000012360 testing method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
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- 238000000137 annealing Methods 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
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- 230000020477 pH reduction Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229960004106 citric acid Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
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- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- 239000002028 Biomass Substances 0.000 description 1
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- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
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- 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 description 1
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/58—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
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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
- 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 an amorphous carbon material modified by carbon points and a preparation method and application thereof, belonging to the technical field of amorphous carbon material preparation. The invention discloses an amorphous carbon material with carbon point modification, which can grow carbon points on the surface and in the interior of amorphous carbon in situ by utilizing various methods such as hydrothermal method, calcination method, coprecipitation method and the like. Carbon points growing on the surface of the amorphous carbon in situ can be induced to generate different SEI films in the sodium storage process, and the carbon points growing inside the amorphous carbon are beneficial to electron conduction and ion diffusion, so that the first coulombic efficiency and the specific capacity of the sodium-ion battery are effectively improved.
Description
Technical Field
The invention belongs to the technical field of amorphous carbon material preparation, and relates to an amorphous carbon material modified by carbon points, and a preparation method and application thereof.
Background
In recent decades, green clean energy has been sought worldwide to replace fossil energy. With the gradual maturity of lithium ion battery technology and the development of novel energy sources such as sodium ion batteries and solar batteries, energy structure transformation steps into an acceleration stage. Lithium ion batteries have been widely used in life, almost replacing traditional lead acid batteries and other disposable batteries. However, the lithium resource is low in content and unevenly distributed on the earth, the lithium price starts to rise sharply with the maturity of lithium electric vehicle technology, and in addition, the earth lithium content is far from meeting the requirement of replacing a complete gasoline vehicle, and the development of a sodium ion battery is inevitable.
The sodium ion battery has a similar sodium storage principle as the lithium ion battery, namely, the ions move between the positive electrode and the negative electrode so as to realize charging and discharging. The negative electrode materials studied at present mainly include alloys, metal compounds, carbon, organic compounds, polyanions, and the like. However, the most possible industrialization-oriented carbon materials are still low in cost and stable in performance. At present, the carbon material mainly comes from biomass carbon and is difficult to realize large-scale preparation. The performance of the asphalt-based carbon and the coal-based carbon with rich yield does not meet the requirements.
Therefore, the search for suitable carbon sources, simple preparation methods and efficient modification strategies has become an urgent need.
Disclosure of Invention
In view of the above, an object of the present invention is to provide an amorphous carbon material modified with carbon dots; the second purpose of the invention is to provide a preparation method of an amorphous carbon material modified by carbon points; the invention also aims to provide application of the amorphous carbon material modified by the carbon dots in preparation of the negative electrode material of the sodium-ion battery.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the amorphous carbon material modified by the carbon dots comprises amorphous carbon and the carbon dots, wherein the carbon dots account for 0.1-10% of the weight of the amorphous carbon, the diameter of the carbon dots is 3-50 nm, and the carbon dots are distributed on the surface and/or inside the amorphous carbon.
2. The preparation method of the amorphous carbon material modified by the carbon points comprises the following steps:
(1) carrying out solvent heat treatment, roasting treatment or microwave radiation treatment on the activated carbon point carbon source and the acid-treated amorphous carbon source to enable carbon points to grow on the surface and/or inside of the amorphous carbon precursor or the amorphous carbon in situ to obtain a carbon point modified amorphous carbon precursor;
(2) and placing the carbon point modified amorphous carbon precursor in a protective atmosphere, heating until the carbon point carbon source is completely carbonized, naturally cooling, and taking out to obtain the carbon point modified amorphous carbon material.
Preferably, the activation treatment is pyrolysis treatment, electrolysis treatment or acid oxidation treatment of the carbon point carbon source;
the pyrolysis treatment is to heat a carbon point carbon source to a pyrolysis temperature and continuously stir for 5-180 min;
the electrolytic treatment is to soak a carbon point carbon source serving as an electrode in an aqueous electrolyte and generate defects by applying an oxidation-reduction potential, or the electrolytic treatment is to dissolve the carbon point carbon source in a solvent, insert two metal electrodes, electrify for 1-30 h under a voltage of 2-50V, and centrifugally collect;
and the acid oxidation treatment is to dissolve the carbon point carbon source in an acid solution, perform water bath ultrasound for 12-200 h, and then perform centrifugation.
Preferably, the amorphous carbon source is treated in the following manner prior to the acid treatment: pyrolyzing an amorphous carbon source at 500-1600 ℃ in an inert atmosphere, and then crushing the carbon source to obtain an acid-treated amorphous carbon source with the particle size of 0.5-500 um;
the acid treatment is to add an amorphous carbon source into an acid solution for heating, then carry out hydrothermal treatment, cool, wash and dry;
the acid solution is any one or more of nitric acid, hydrochloric acid or sulfuric acid.
Preferably, the amorphous carbon source is any one or more of pitch, coal tar, glucose monohydrate, sucrose, starch, lignin, cellulose, charcoal, phenolic resin, sodium polyacrylate, polytetrafluoroethylene or urea;
the carbon point carbon source is any one or more of animal hair, plant fiber, carbon fiber, graphene, graphite, anthracite, coke, carbon nano tube, urea, citric acid, glucose, monohydrate glucose, sucrose, starch, lignin, protein and vitamin;
the mass ratio of the amorphous carbon source to the carbon point carbon source is 1: 0.1-1: 10.
Preferably, the solvent heat treatment specifically comprises: dispersing the amorphous carbon source subjected to acid treatment in a solvent, adding a carbon point carbon source, dissolving, then placing in a reaction kettle, sealing, preserving heat at 100-250 ℃ for 1-15 h, cooling, washing and drying;
the solvent is any one or more of water, formamide, isopropanol, N-dimethylformamide, N-methylpyrrolidone or acetone.
Preferably, the roasting treatment is to heat the carbon point carbon source to be molten, add the amorphous carbon source under stirring, and stir until the mixture is uniformly mixed.
Preferably, the microwave radiation treatment specifically comprises: dispersing an amorphous carbon or an amorphous carbon source in a solvent, adding a carbon point carbon source, dissolving, and then placing in a microwave reactor for reaction, wherein the power in the microwave reactor is 200-1000W, the temperature is 60-200 ℃, and the reaction time is 20-120 min.
Preferably, in the step (2), the protective atmosphere is an atmosphere formed by any one or more of argon, nitrogen, ammonia gas or hydrogen-argon mixed gas, and the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 5: 95-10: 90;
the carbonization is specifically as follows: heating to 100-1600 ℃ at the speed of 0.5-10 ℃/min, and then carrying out thermal pyrolysis for 1-10 h.
3. The amorphous carbon material modified by the carbon dots is applied to the preparation of the cathode material of the sodium-ion battery.
The invention has the beneficial effects that: the invention discloses an amorphous carbon material modified by carbon dots, which is characterized in that the carbon dots with the weight percentage of 0.1-10% and the diameter of 5-50 nm are distributed on the surface and/or inside the amorphous carbon. The carbon points are mainly crystal carbon with good crystallinity, the formation of the SEI film is influenced to a certain extent by utilizing different graphitization degrees, the crystal carbon grows on the surface of amorphous carbon and is beneficial to improving the contents of inorganic salt and organic matters of the SEI film, sodium ions can rapidly penetrate through the SEI film by increasing the inorganic salt under a proper condition through regulating and controlling the proportion, the ionic impedance and the interface charge transfer impedance are reduced, the content of organic components is increased, the mechanical property of the SEI film can be improved, the SEI film is prevented from being damaged by volume expansion, the continuous dissolution of the inorganic components in electrolyte is slowed, and the cycle performance is improved; in addition, the growth of carbon points with higher graphitization degree on the surface of the amorphous carbon reduces specific surface area and surface defects, so that the first coulombic efficiency of the sodium-ion battery is effectively improved. The carbon dots grown in the amorphous carbon are beneficial to the transmission of ions in the bulk phase, and meanwhile, the electronic conductivity is increased, and compared with the unmodified amorphous carbon material, the ion diffusion is greatly improved. The carbon-point-modified amorphous carbon material has the advantages of small specific surface area, few surface defects, higher ion diffusion rate, small charge transfer interface impedance and good SEI film ion conductivity, can be widely applied to preparation of sodium ion battery electrode materials, ensures the increase of the first coulombic efficiency of the material, and effectively improves the specific capacity and the rate capability.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a comparison XRD plot of carbon dot modified amorphous carbon material (nitrogen doped carbon dot modified asphaltic amorphous carbon material (CDMP)) prepared in example 1 and pure asphaltic amorphous carbon (PP) prepared in comparative example 1;
fig. 2 is a graph comparing electrochemical charge and discharge curves (a) and cycle performance (b) at room temperature for a button cell prepared from the carbon dot modified amorphous carbon material (nitrogen doped carbon dot modified pitch based amorphous carbon material (CDMP)) prepared by the method of example 1 and the pure pitch based amorphous carbon (PP) prepared in comparative example 1;
FIG. 3 is a TEM image of a carbon site modified amorphous carbon material (CDMC) (a, b) and a pure hard carbon material (HC) (c) prepared in example 2;
fig. 4 is a graph comparing electrochemical charge and discharge curves at room temperature for button cells prepared from the carbon dot modified amorphous carbon material (CDMC) prepared in example 2 and the pure hard carbon material (HC) prepared in comparative example 2;
fig. 5 is a Raman comparison graph of amorphous carbon material modified with graphene quantum dots (GDMC) prepared in example 3 and soft carbon without graphene quantum dots modification (SC) prepared in comparative example 3;
fig. 6 is a graph (a) showing cycle performance and rate performance at room temperature of an amorphous carbon material (GDMC) modified with graphene quantum dots in example 3 and Soft Carbon (SC) without graphene quantum dots modification prepared in comparative example 3;
FIG. 7 is a SEM comparison of carbon site modified soft carbon (CDSC) (a) prepared by the roasting process in example 4 and pure pitch-based amorphous carbon (PP) (b) prepared in comparative example 4;
fig. 8 is a charge and discharge curve of the soft carbon modified with Carbon Dots (CDSC) in example 4 and the pure pitch-based amorphous carbon (PP) prepared in comparative example 4.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
A carbon point modified amorphous carbon material (nitrogen-doped carbon point modified asphalt-based amorphous carbon material) is prepared by the following steps:
(1) and (2) placing 2g of asphalt as an amorphous carbon source in a high-temperature tubular furnace for annealing treatment under the argon protective atmosphere, wherein the gas flow is 50mL/min, the heating rate is 5 ℃/min, heating to 800 ℃, keeping the temperature for 2h, and taking out the asphalt after the asphalt is naturally cooled to room temperature to obtain a product, thereby obtaining the pure asphalt-based amorphous carbon material.
(2) Putting the pure asphalt-based amorphous carbon material into a planetary ball mill for grinding (ball milling is carried out for 2 hours at the rotating speed of 600 rpm) until the particle size is 0.5-500 um, then putting the amorphous carbon powder obtained by ball milling into a 3.5mol/L nitric acid solution, stirring for 30min, carrying out hydrothermal treatment for 1.5 hours at the temperature of 160 ℃, taking out a product after naturally cooling to the normal temperature, carrying out suction filtration and washing for 3 times by using 1000mL deionized water, and drying in a blast drying oven at the temperature of 60 ℃ overnight to obtain the amorphous carbon material subjected to hydrothermal acidification treatment.
(3) Placing the amorphous carbon material subjected to the hydrothermal acidification treatment in 40mL of formamide solvent for uniform dispersion, adding 2g of urea as a carbon point carbon source, stirring and mixing uniformly, placing the mixture in a reaction kettle for sealing, performing hydrothermal treatment at 200 ℃ for 5 hours, naturally cooling to normal temperature, taking out a product, performing suction filtration and washing for 3 times by using 1000mL of deionized water and ethanol, and drying in a forced air drying oven at 60 ℃ overnight to obtain the carbon point modified amorphous carbon precursor.
(4) And (2) placing the carbon-point-modified amorphous carbon precursor into a high-temperature tube furnace to perform annealing treatment under the argon protective atmosphere (the gas flow is 50mL/min, the heating rate is 5 ℃/min, the temperature is increased to 800 ℃ and is kept for 1h), and taking out after the precursor is naturally cooled to room temperature, thus obtaining the carbon-point-modified amorphous carbon material (nitrogen-doped carbon-point-modified pitch-based amorphous carbon material (CDMP)).
Comparative example 1
Pure pitch was subjected to only the step (1) of example 1 to obtain pure pitch-based amorphous carbon (PP).
Performance testing
Fig. 1 is a XRD comparison graph of the carbon dot modified amorphous carbon material (nitrogen doped carbon dot modified pitch based amorphous carbon material (CDMP)) prepared in example 1 and the pure pitch based amorphous carbon (PP) prepared in comparative example 1. As can be seen from FIG. 1, CDMP and PP both have two distinct characteristic peaks, which respectively correspond to the (002) crystal face and the (100) crystal face of the disordered carbon material, but since the size of the carbon dots is only nanoscale and the content is small, no distinct graphite characteristic peak is detected.
The carbon dot modified amorphous carbon material prepared in example 1 (nitrogen doped carbon dot modified pitch based amorphous carbon material (CDMP)) and the pure pitch based amorphous carbon (PP) prepared in comparative example 1 were used to prepare a sodium ion battery to test the performance thereof, and the specific procedures are as follows:
(1) respectively mixing and grinding the carbon dot modified amorphous carbon material prepared in example 1 (nitrogen-doped carbon dot modified asphalt-based amorphous carbon material (CDMP)) and the pure asphalt-based amorphous carbon (PP) prepared in comparative example 1 with sodium alginate in a mass ratio of 9:1, and adding deionized water for wet grinding until the slurry can pass through a 200-mesh stainless steel screen;
(2) respectively coating the two kinds of slurry ground in the step (1) on copper foil by using a wet film coater, controlling the thickness to be 200 mu m, and then transferring the copper foil to a vacuum oven at 120 ℃ for drying for 12 h;
(3) cutting the two pole pieces in the step (2) into 12mm small round pieces, transferring the small round pieces into a glove box filled with argon, and adding 150 mu L of electrolyte to assemble the button cell (the model of the button cell is CR2032, the diaphragm is a glass fiber diaphragm, and the electrolyte is 1M NaPF 6 Ethylene carbonate and dimethyl carbonate (1: 1)).
(4) After the assembly, the two button cells were removed from the glove box, left to stand at room temperature for 8 hours, and then subjected to electrochemical performance testing on a LAND cell testing system.
Fig. 2 is a graph comparing electrochemical charge and discharge curves (a) and cycle performance (b) at room temperature for a button cell prepared from the carbon dot modified amorphous carbon material (nitrogen doped carbon dot modified pitch based amorphous carbon material (CDMP)) prepared by the method of example 1 and the pure pitch based amorphous carbon (PP) prepared in comparative example 1. As can be seen from fig. 2, the carbon dot modified amorphous carbon material (nitrogen doped carbon dot modified asphaltic amorphous carbon material (CDMP)) prepared in example 1 exhibited higher krf capacity and first coulombic efficiency in the constant current charge and discharge test, compared to the pure asphaltic amorphous carbon (PP) prepared in comparative example 1. The specific gram capacities of the carbon dot modified amorphous carbon material prepared in example 1 (nitrogen doped carbon dot modified pitch based amorphous carbon material (CDMP)) and the pure pitch based amorphous carbon (PP) prepared in comparative example 1 were 409.0mAh/g and 199.7mAh/g, respectively, and the first coulombic efficiencies were 76.10% and 65.82%, respectively, at a current density of 30 mA/g. The overall disorder of the microstructure is beneficial to the storage of sodium ions, but also is not beneficial to the first coulombic efficiency and the ion and electron transmission, so that the distribution of the nanoscale ordering in the disordered carbon and the surface of the disordered carbon is very significant to the improvement of the reaction kinetics of the disordered carbon.
Example 2
A carbon point modified amorphous carbon material (boron-doped carbon point modified hard carbon) is prepared by the following steps:
(1) and (2) putting 2g of glucose as an amorphous carbon source in a high-temperature tube furnace for annealing treatment under the argon protective atmosphere, wherein the gas flow is 50mL/min, the heating rate is 5 ℃/min, heating to 1200 ℃, keeping the temperature for 2h, and taking out the amorphous carbon source after naturally cooling to room temperature to obtain a product, thereby obtaining the amorphous carbon material.
(2) Placing the amorphous carbon material in a planetary ball mill for grinding (ball milling for 2h at the rotating speed of 600 rpm) until the particle size is 0.5-500 um, then placing the hard carbon powder obtained by ball milling in a 3.5mol/L nitric acid solution for stirring for 30min, carrying out hydrothermal treatment for 1.5h under the reaction condition of 160 ℃, taking out a product after naturally cooling to the normal temperature, carrying out suction filtration and washing for 3 times by using 1000mL deionized water, and drying in a blast drying oven at 60 ℃ overnight to obtain the amorphous carbon material subjected to hydrothermal acidification treatment.
(3) Placing the amorphous carbon material subjected to the hydrothermal acidification treatment in 40mL of formamide solvent for uniform dispersion, adding 2g of anhydrous citric acid as a carbon point carbon source, adding 1g of boric acid and sodium borate as boron atom dopants, stirring until the boric acid and the sodium borate are completely dissolved, carrying out hydrothermal reaction at 200 ℃ for 5 hours, naturally cooling to the normal temperature, taking out, carrying out suction filtration and washing for 3 times by using 1000mL of deionized water and ethanol, and drying in a forced air drying oven at 60 ℃ overnight to obtain the carbon point modified amorphous carbon precursor.
(4) And (2) placing the precursor in a high-temperature tube furnace to carry out annealing treatment under the argon protective atmosphere (the gas flow is 50mL/min, the heating rate is 5 ℃/min, heating to 1200 ℃ and keeping the temperature for 1h), and taking out the precursor after naturally cooling to room temperature to obtain a product, thus obtaining the carbon-modified amorphous carbon material (CDMC).
Comparative example 2
Glucose was subjected to only the treatment of the step (1) in example 2 to obtain pure hard carbon material (HC).
Performance testing
Fig. 3 is a TEM image of an amorphous carbon material modified with Carbon Dots (CDMC) (a, b) and a pure hard carbon material (c) prepared in example 2. From fig. 3, it can be seen that carbon points are combined with hard carbon, the carbon points are distributed in a dispersed manner and do not agglomerate, the particle size distribution of the carbon points is about 10-20 nm, obvious lattice stripes can be seen, the spacing between crystal planes is 0.22nm, and the spacing is consistent with that of common carbon points; pure hard carbon materials have regularly arranged, curved carbon layers. The difference in microstructure results in differences in their properties.
An electrode and a sodium ion battery were manufactured using the carbon dot modified amorphous carbon material (CDMC) prepared in example 2 and the pure hard carbon material (HC) prepared in comparative example 2 according to the method for testing the performance of the product in example 1, except that the ester electrolyte was changed to NaPF6 dimethyl ether, and a comparative graph of electrochemical charge and discharge curves at room temperature of the coin battery manufactured using the carbon dot modified amorphous carbon material (CDMC) prepared in example 2 and the pure hard carbon material (HC) prepared in comparative example 2 was shown in fig. 4. From the results of fig. 4, it can be seen that: under the current density of 30mA/g, compared with a pure hard carbon material (HC), the carbon dot modified amorphous carbon material (CDMC) and the pure hard carbon material (HC) show similar first discharge capacity which is more than 450mAh/g, and the platform capacities are almost overlapped, which shows that the modification of the carbon dots hardly influences the intercalation of sodium ions; however, the carbon-point modified amorphous carbon material (CDMC) showed higher average voltage and slightly higher capacity at the slope, indicating that the carbon point may have some influence on the adsorption capacity of sodium ions. This may be related to the surface heterogeneity, reactive groups and boundary effects possessed by the carbon dots themselves, but higher average voltages are detrimental to the full cell energy density. In addition, the first coulombic efficiency of the carbon-point-modified hard carbon is improved to a certain extent, which may have a certain relation with the reduction of surface defects and specific surface area.
Example 3
A carbon dot modified amorphous carbon material (graphene quantum dot modified soft carbon) is prepared by the following steps:
(1) placing 2g of anthracite coal as an amorphous carbon source in a high-temperature tubular furnace for annealing treatment under the argon protective atmosphere (the gas flow is 50mL/min, the heating rate is 5 ℃/min, heating to 800 ℃ and keeping the temperature for 2h), and taking out the anthracite coal after naturally cooling to room temperature to obtain a product, thereby obtaining the pure pitch-based amorphous carbon material.
(2) The amorphous carbon material is placed in a planetary ball mill to be subjected to crushing treatment (the rotating speed is 600rpm, the ball milling is carried out for 2 hours) until the particle size is 0.5-500 um, then the amorphous carbon powder obtained through ball milling is placed in a 3.5mol/L nitric acid solution to be stirred for 30min, hydrothermal treatment is carried out for 1.5 hours at 160 ℃, after the amorphous carbon powder is naturally cooled to the normal temperature, a product is taken out, is subjected to suction filtration and washing for 3 times by using 1000mL deionized water, and is dried in a 60 ℃ forced air drying oven overnight, so that the amorphous carbon material subjected to hydrothermal acidification treatment is obtained.
(3) Placing the amorphous carbon material subjected to the hydrothermal acidification treatment in 40mL of deionized water solvent for uniform dispersion, adding 1g of starch as a carbon point carbon source, stirring for 15min at 60 ℃, quickly pouring into a 100mL of polytetrafluoroethylene high-pressure reaction kettle after complete dissolution, carrying out hydrothermal treatment at 190 ℃ for 2h, naturally cooling to normal temperature, taking out the product, carrying out suction filtration and washing for 3 times by using 1000mL of deionized water and ethanol, and drying in a 60 ℃ forced air drying oven overnight to obtain the amorphous carbon precursor modified by the graphene quantum dots.
(4) And (2) placing the precursor in a high-temperature tube furnace, annealing under the argon protective atmosphere (the gas flow is 50mL/min, the heating rate is 5 ℃/min, heating to 800 ℃ and keeping the temperature for 1h), naturally cooling to room temperature, and taking out to obtain a product, thereby obtaining the amorphous carbon material (GDMC) modified by the graphene quantum dots.
Comparative example 3
The anthracite is only treated in the step (1) in the example 3, and the Soft Carbon (SC) which is not modified by the graphene quantum dots is obtained.
Performance testing
Fig. 5 is a Raman comparison graph of the amorphous carbon material modified with graphene quantum dots (GDMC) prepared in example 3 and the soft carbon not modified with graphene quantum dots (SC) prepared in comparative example 3. As can be seen in FIG. 5, both materials exhibit broader D and G peaks, indicating that both carbon materials contain a more defective SP at the same time 3 Carbon and SP with high degree of graphitization 2 Carbon. Through careful analysis, it was found that I of the amorphous carbon material modified with graphene quantum dots (GDMC) prepared in example 3 was compared to that of the comparative material (SC) prepared in comparative example 3 D /I G Slightly smaller, indicating a higher degree of order, probably due to the fact that the amorphous carbon phase contains more highly crystalline graphene quantum dots.
The amorphous carbon material modified with graphene quantum dots (GDMC) in example 3 and the Soft Carbon (SC) without graphene quantum dots modification prepared in comparative example 3 were prepared into an electrode and a sodium ion battery according to the performance test method of the product prepared in example 1, and then subjected to a temperature of 10C (1C-300 mAh g) -1 ) The electrochemical test is carried out under the high current density, and the multiplying power performance test is carried out under different current densities. FIG. 6 is a graph of the structure of graphene in example 3The cycle performance (a) and rate performance graph (b) of the quantum dot modified amorphous carbon material (GDMC) and the Soft Carbon (SC) without graphene quantum dot modification prepared in comparative example 3 at room temperature. As can be seen from fig. 6, under a large current density of 10C, the capacities of both are only about 1/3 of the theoretical specific capacities, which indicates that the rate capability is poor, and indicates that the soft carbon prepared in example 4 has a poor ion diffusion rate, and in addition, may have a certain relationship with the poor ion diffusion rate of the ester electrolyte. Through rate performance tests, the soft carbon modified by the graphene quantum dots shows higher specific capacity under the current densities of 30, 50, 300, 600, 1500 and 3000 mA/g. The specific capacity of the soft carbon (amorphous carbon material (GDMC) modified by the graphene quantum dots is improved to a certain extent, and the graphene quantum dots cannot store sodium due to the small interlayer spacing, so that the ion diffusion rate and the electronic conductivity of the graphene quantum dots are improved.
Example 4
A carbon point modified amorphous carbon material (carbon point modified soft carbon prepared by a roasting method) specifically comprises the following steps:
(1) 2g of citric acid as a carbon point carbon source is ground until no granular sensation exists, then the mixture is placed in a beaker and heated at 250 ℃ for 15min, and is vigorously stirred by a glass rod, so that the molten citric acid as an amorphous carbon material is obtained, and a large amount of carbon points are generated in the process.
(2) And (3) adding 2g of pitch into the molten citric acid obtained in the step (1), and violently stirring to uniformly mix the pitch and the citric acid to obtain the carbon point modified amorphous carbon precursor.
(3) And (3) placing the carbon-point-modified amorphous carbon precursor obtained in the step (2) in a high-temperature tube furnace for annealing treatment under the argon protective atmosphere (the gas flow is 50mL/min, the heating rate is 5 ℃/min, the temperature is increased to 800 ℃ and kept for 2h), and taking out the precursor after the precursor is naturally cooled to room temperature to obtain a product, thus obtaining the carbon-point-modified soft carbon (CDSC) prepared by a roasting method.
Comparative example 4
Pure pitch was subjected to only the step (1) of example 1 to obtain pure pitch-based amorphous carbon (PP).
Performance testing
Fig. 7 is a SEM comparison graph of carbon site modified soft carbon (CDSC) (a) prepared by the baking process in example 4 and pure pitch-based amorphous carbon (PP) (b) prepared in comparative example 4. As can be seen from fig. 7, the soft carbon (CDSC) modified with carbon points prepared by the firing method in example 4 has a rougher surface and more uniform protrusions, compared to the pure pitch-based amorphous carbon (PP) in comparative example 4, which may be caused by uniform bonding of carbon points and pitches.
Electrodes and sodium ion batteries were prepared by testing the performance of example 1 using the soft carbon modified with Carbon Dots (CDSC) of example 4 and the pure pitch-based amorphous carbon (PP) prepared in comparative example 4, and then measured at 0.1C (1C 300mAh g) -1 ) The electrochemical test was carried out at the current density of (1), and the charge-discharge curve is shown in FIG. 8. At the current density of 0.1C, the ramp capacity and the first effect are both obviously improved. In combination with the previous examples, it is assumed that the carbon dots have the effect on the slope capacity and the first effect of the soft carbon, and it is assumed that the reason for the increase of the slope capacity is probably that the distribution of the carbon dots on the amorphous carbon improves the ion diffusion capacity and the electron conductivity, and the reason for the increase of the first effect is probably that the carbon dots with high graphitization degree reduce the surface open pores and defects of the amorphous carbon.
Similarly, the amorphous carbon source in the above embodiment may be any one or more of pitch, coal tar, glucose, monohydrate glucose, sucrose, starch, lignin, cellulose, charcoal, phenolic resin, sodium polyacrylate, polytetrafluoroethylene, or urea; the carbon point carbon source can be any one or more of animal hair, plant fiber, carbon fiber, graphene, graphite, anthracite, coke, carbon nano tube, urea, citric acid, monohydrate glucose, sucrose, starch, lignin, protein and vitamin; the solvent can be any one or more of water, formamide, isopropanol, N-dimethylformamide, N-methylpyrrolidone or acetone; the heat treatment mode can be solvothermal at the temperature of 100-250 ℃, pyrolysis at the temperature of 500-1500 ℃ in an inert atmosphere, and heating evaporation at the temperature of 40-100 ℃, wherein the inert atmosphere is any one or more of argon, nitrogen, ammonia gas or hydrogen-argon mixed gas (the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 5: 95-10: 90). The carbon quantum dot dopant can be a nonmetallic compound containing any one or more of boron, nitrogen, oxygen, fluorine, phosphorus or sulfur (such as any one or more of boric acid, sodium borohydride, urea, melamine, chitosan, polytetrafluoroethylene, polyvinylidene fluoride, sodium polyacrylate, ammonium dihydrogen phosphate, phytic acid, thiourea or sodium dodecyl benzene sulfonate), the carbon quantum dot can be a graphite carbon dot, an amorphous carbon dot or a morphology-modified amorphous carbon material with the coexistence of the graphite carbon dot and the amorphous carbon dot, test results of the formed amorphous carbon material modified by the carbon dots are shown in the above embodiment, the amorphous carbon material has the advantages of high electronic conductivity, fast ion diffusion, small interface impedance and the like, and can be widely used for preparing sodium ion battery electrode materials.
In summary, the present invention discloses an amorphous carbon material modified by carbon dots, wherein the material comprises 0.1-10 wt% of carbon dots with a diameter of 5-50 nm distributed on the surface and/or inside the amorphous carbon. The carbon dots are mainly crystal carbon with good crystallinity, the formation of the SEI film is influenced to a certain extent by utilizing different graphitization degrees, the content of inorganic salt and organic matter of the SEI film is favorably improved when the carbon dots grow on the surface of amorphous carbon, the inorganic salt is increased under a proper condition by regulating and controlling the proportion, sodium ions can rapidly penetrate through the SEI film, the ionic resistance and the interface charge transfer resistance are reduced, the content of organic components is increased, the mechanical property of the SEI film can be improved, the damage of volume expansion to the SEI film is prevented, the continuous dissolution of the inorganic components in electrolyte is slowed down, and the cycle performance is improved; in addition, the growth of carbon points with higher graphitization degree on the surface of the amorphous carbon reduces the specific surface area and the surface defects, so that the first coulombic efficiency of the sodium-ion battery is effectively improved. The carbon dots grown in the amorphous carbon are beneficial to the transmission of ions in the bulk phase, and meanwhile, the electronic conductivity is increased, and compared with the unmodified amorphous carbon material, the ion diffusion is greatly improved. The carbon-point-modified amorphous carbon material has the advantages of small specific surface area, few surface defects, high ion diffusion rate, small charge transfer interface impedance and good SEI film ion conductivity, can be widely applied to preparation of sodium ion battery electrode materials, ensures the increase of the first coulombic efficiency of the material, and effectively improves the specific capacity and the rate capability.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The amorphous carbon material modified by carbon dots is characterized by comprising amorphous carbon and carbon dots, wherein the weight percentage of the carbon dots in the amorphous carbon is 0.1-10%, the diameter of the carbon dots is 3-50 nm, and the carbon dots are distributed on the surface and/or inside the amorphous carbon.
2. The method of preparing the carbon dot-modified amorphous carbon material as claimed in claim 1, wherein the method comprises the steps of:
(1) carrying out solvent heat treatment, roasting treatment or microwave radiation treatment on the activated carbon point carbon source and the acid-treated amorphous carbon source to enable carbon points to grow on the surface and/or inside of the amorphous carbon precursor or the amorphous carbon in situ to obtain a carbon point modified amorphous carbon precursor;
(2) and placing the carbon point modified amorphous carbon precursor in a protective atmosphere, heating until the carbon point carbon source is completely carbonized, naturally cooling, and taking out to obtain the carbon point modified amorphous carbon material.
3. The production method according to claim 2, wherein the activation treatment is a pyrolysis treatment, an electrolysis treatment or an acid oxidation treatment of a carbon point carbon source;
the pyrolysis treatment is to heat the carbon source to a pyrolysis temperature and continuously stir for 5-180 min;
the electrolytic treatment is to soak a carbon point carbon source serving as an electrode in an aqueous electrolyte and generate defects by applying an oxidation-reduction potential, or the electrolytic treatment is to dissolve the carbon point carbon source in a solvent, insert two metal electrodes, electrify for 1-30 h under the voltage of 2-50V, and centrifugally collect;
and the acid oxidation treatment is to dissolve the carbon point carbon source in an acid solution, perform water bath ultrasound for 12-200 h, and then perform centrifugation.
4. The method for preparing as claimed in claim 2, wherein the amorphous carbon source is treated before the acid treatment in the following manner: pyrolyzing an amorphous carbon source at 500-1600 ℃ in an inert atmosphere, and then crushing the carbon source to obtain an acid-treated amorphous carbon source with the particle size of 0.5-500 um;
the acid treatment is to add an amorphous carbon source into an acid solution for heating, then carry out hydrothermal treatment, cool, wash and dry; the acid solution is any one or more of nitric acid, hydrochloric acid or sulfuric acid.
5. The preparation method according to claim 2, wherein the amorphous carbon source is any one or more of pitch, coal tar, glucose monohydrate, sucrose, starch, lignin, cellulose, charcoal, phenolic resin, sodium polyacrylate, polytetrafluoroethylene or urea;
the carbon point carbon source is any one or more of animal hair, plant fiber, carbon fiber, graphene, graphite, anthracite, coke, carbon nano tube, urea, citric acid, glucose, monohydrate glucose, sucrose, starch, lignin, protein and vitamin;
the mass ratio of the amorphous carbon source to the carbon point carbon source is 1: 0.1-1: 10.
6. The preparation method according to claim 2, wherein the solvothermal treatment is specifically: dispersing the amorphous carbon source subjected to acid treatment in a solvent, adding a carbon point carbon source, dissolving, then placing in a reaction kettle, sealing, preserving heat at 100-250 ℃ for 1-15 h, cooling, washing and drying;
the solvent is any one or more of water, formamide, isopropanol, N-dimethylformamide, N-methylpyrrolidone or acetone.
7. The preparation method according to claim 2, wherein the baking treatment is heating the carbon point carbon source to be molten, adding the amorphous carbon source under stirring, and stirring until the mixture is uniformly mixed.
8. The preparation method according to claim 2, wherein the microwave radiation treatment is specifically: dispersing amorphous carbon or an amorphous carbon source in a solvent, adding a carbon point carbon source, dissolving, and then placing in a microwave reactor for reaction, wherein the power in the microwave reactor is 200-1000W, the temperature is 60-200 ℃, and the reaction time is 20-120 min.
9. The preparation method according to claim 2, wherein in the step (2), the protective atmosphere is an atmosphere formed by any one or more of argon, nitrogen, ammonia gas or a hydrogen-argon mixed gas, and the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 5: 95-10: 90;
the carbonization is specifically as follows: heating to 100-1600 ℃ at the speed of 0.5-10 ℃/min, and then carrying out thermal pyrolysis for 1-10 h.
10. The use of the carbon dot modified amorphous carbon material of claim 1 in the preparation of a negative electrode material for sodium ion batteries.
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