CN117142464A - Preparation process of high-capacity graphite anode material - Google Patents
Preparation process of high-capacity graphite anode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 32
- 239000010439 graphite Substances 0.000 title claims abstract description 32
- 239000010405 anode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 60
- 239000002105 nanoparticle Substances 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000008367 deionised water Substances 0.000 claims abstract description 48
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000002791 soaking Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000006260 foam Substances 0.000 claims abstract description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000000502 dialysis Methods 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 104
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 96
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- 239000004317 sodium nitrate Substances 0.000 claims description 12
- 235000010344 sodium nitrate Nutrition 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000001354 calcination Methods 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 241000923606 Schistes Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- C01B32/194—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation process of a high-capacity graphite anode material, which belongs to the field of lithium ion battery anode materials and comprises the following steps: preparing graphene sheets from natural graphite, adding the graphene sheets into absolute ethyl alcohol, uniformly stirring for 15min, transferring into a reaction kettle, heating, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, adding modified nano particles, uniformly stirring for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h, preparing gel after three times of replacement, transferring into an ethanol water solution with the volume fraction of 15% for dialysis for 6h, drying, preparing a foam precursor, sending into a tubular furnace, and calcining for 2h at 550 ℃ to prepare a graphite anode material; the special structure can give higher capacity, and the graphene of the structure can effectively relieve the problem of volume expansion in the charge and discharge process due to the porous characteristic of the graphene, so that the battery is helped to realize longer and stable charge and discharge cycle.
Description
Technical Field
The invention relates to the field of lithium ion battery negative electrode materials, in particular to a preparation process of a high-capacity graphite negative electrode material.
Background
Lithium ion battery anode materials can be generally divided into two main categories, namely carbon materials and non-carbon materials; carbon materials include graphitic, non-graphitic, and nanostructured carbon-based anode materials. The carbon material has the characteristics of environmental friendliness, low cost, high specific capacity, good cycle performance, long service life, low chemical potential and the like, wherein graphite is the anode material with the highest commercialization degree at present.
Natural graphite is graphite naturally formed in nature, and generally appears in the form of graphite schist, graphite gneiss, graphite-containing schist, modified shale and other ores, and in the process of lithium ion intercalation and deintercalation, the existing natural graphite products are easy to cause stripping problems due to volume expansion, so that the battery capacity is seriously attenuated and even potential safety hazards are generated. The artificial graphite material has the problems of difficult processing and low battery capacity and compaction density in the pulping process of the cathode due to larger interlayer spacing, low graphitization degree, rough surface, increased defects and larger specific surface area; in order to obtain an ideal product with higher capacity and higher compaction density, the comprehensive performance of the product is generally improved by modifying graphite during the processing of artificial graphite.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation process of a high-capacity graphite anode material.
The aim of the invention can be achieved by the following technical scheme:
a preparation process of a high-capacity graphite anode material comprises the following steps:
adding natural graphite and sodium nitrate into concentrated sulfuric acid, adding potassium permanganate under ice water bath, uniformly stirring for 1h, then adding deionized water, heating to 90 ℃, continuously stirring for 30min, then adding 30% hydrogen peroxide aqueous solution by mass fraction, uniformly stirring and reacting for 30min, centrifuging, respectively washing three times with 15% dilute hydrochloric acid by mass fraction and deionized water, and drying to obtain graphene sheets;
and secondly, adding graphene sheets into absolute ethyl alcohol, uniformly stirring for 15min, transferring into a reaction kettle, heating to 200 ℃, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, adding modified nano particles, uniformly stirring for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h for three times to obtain gel, transferring into a 15% ethanol water solution for dialysis for 6h, drying to obtain a foam precursor, and sending into a tubular furnace to calcine for 2h at 550 ℃ to obtain the graphite anode material.
The preparation method comprises the steps of firstly preparing graphene by treating natural graphite with a strong oxidant and concentrated acid, leading oxygen-containing functional groups to the surface of the graphene so that the graphene is negatively charged, secondly preparing three-dimensional graphene foam under the condition of not adding a reducing agent by a solvothermal method and a high-temperature calcination method, wherein the graphene with the structure can effectively relieve the problem of volume expansion due to the porous characteristic of the graphene in the charge-discharge process, and helps a battery realize longer and stable charge-discharge cycle.
Further: the dosage ratio of the natural graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate, deionized water and aqueous hydrogen peroxide solution in the first step is controlled to be 1g to 50mL to 2-4g to 100mL to 20mL, and the dosage ratio of the graphene sheets, the modified nano particles, the absolute ethyl alcohol and the soaking solution in the second step is controlled to be 2-5mg to 0.1-0.3mg to 10-20mL to 150mL.
Further: the soaking solution is formed by mixing acetone, absolute ethyl alcohol and deionized water according to the volume ratio of 1:1:1.
Further: the modified nanoparticle comprises the following steps:
step S1, adding nickel chloride hexahydrate into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10 minutes to obtain a solution a; adding sulfur powder into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10min to obtain a solution b; adding the solution b into the solution a while stirring, adding an ethylene glycol solution of polyvinylpyrrolidone, continuously stirring for 30min, heating to 200 ℃, preserving heat and uniformly stirring for 12h, filtering after the reaction is finished, respectively washing for three times by using deionized water and absolute ethyl alcohol, and drying to obtain nano particles;
in the step S1, nickel chloride hexahydrate and sulfur powder are used as raw materials to prepare nano particles which are NiS2 nano particles, and the nano particles are introduced into a battery anode material to form nano structures, so that the volume change generated in the circulation process can be reduced, the diffusion rate of lithium ions and sodium ions can be accelerated, the circulation stability and the rate capability are improved, and the ultra-small nano particles are extremely easy to agglomerate and are unevenly distributed, so that the influence on the performance is larger.
S2, adding the prepared nano particles into an ethanol water solution with the volume fraction of 10%, adding aminopropyl trimethoxy silane, magnetically stirring, heating and refluxing, and carrying out reflux reaction for 12 hours to obtain modified nano particles;
step S2, adding electropositive aminopropyl trimethoxy silane, and enabling the surface of the nanoparticle to have positive charges through reflux reaction;
further: in the step S1, the dosage ratio of the nickel chloride hexahydrate to the ethylene glycol solution in the solution a is 0.65-0.70 g:35-37.5 mL, and the dosage ratio of the sulfur powder to the ethylene glycol solution in the solution b is 0.152-0.158 g:35-37.5 mL.
Further: the polyethylene glycol solution of the polyvinylpyrrolidone in the step S1 is prepared by mixing the polyvinylpyrrolidone and the ethylene glycol according to the dosage ratio of 1.2-1.4 g:37.5-38 mL for 10 min.
Further: in the step S2, the weight ratio of the nano particles, the aminopropyl trimethoxysilane and the absolute ethyl alcohol is controlled to be 1:1-1.2:20.
The invention has the beneficial effects that:
according to the preparation method, the graphene anode material is prepared by treating natural graphite through a strong oxidant and concentrated acid, the graphene is prepared, oxygen-containing functional groups are introduced into the surface of the graphene to enable the graphene to be negatively charged, a three-dimensional graphene foam is prepared under the condition that a reducing agent is not added through a solvothermal method and a high-temperature calcination method, a special structure can be endowed with higher capacity, the graphene of the structure can effectively relieve the problem of volume expansion due to the porous characteristic of the graphene, the battery can realize longer and stable charge-discharge circulation, the unique graphene layer stacked structure and the porous structure can establish a three-dimensional conductive network to promote rapid charge-discharge reaction through ion and electron channels, and modified nano particles are added in the process.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation process of a high-capacity graphite anode material comprises the following steps:
adding natural graphite and sodium nitrate into concentrated sulfuric acid, adding potassium permanganate under ice water bath, stirring at a constant speed for 1h, then adding deionized water, heating to 90 ℃, continuing stirring for 30min, then adding 30% by mass of hydrogen peroxide aqueous solution, stirring at a constant speed, reacting for 30min, centrifuging, respectively washing three times with 15% by mass of dilute hydrochloric acid and deionized water, and drying to obtain graphene sheets, wherein the dosage ratio of the natural graphite to the sodium nitrate to the concentrated sulfuric acid to the potassium permanganate to the deionized water to the hydrogen peroxide aqueous solution is 1 g:1 g:50 mL:2 g:100 mL:20 mL;
adding graphene sheets into absolute ethyl alcohol, uniformly stirring for 15min, transferring into a reaction kettle, heating to 200 ℃, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, adding modified nano particles, uniformly stirring for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h for three times to obtain gel, transferring into an ethanol aqueous solution with the volume fraction of 15% for dialysis for 6h, drying to obtain a foam precursor, sending into a tubular furnace, calcining for 2h at 550 ℃, and obtaining a graphite anode material, wherein the dosage ratio of the graphene sheets, the modified nano particles, the absolute ethyl alcohol and the soaking solution is2 mg:0.1 mg:10 mL:150 mL.
The soaking solution is formed by mixing acetone, absolute ethyl alcohol and deionized water according to the volume ratio of 1:1:1.
The modified nanoparticle comprises the following steps:
step S1, adding nickel chloride hexahydrate into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10 minutes to obtain a solution a; adding sulfur powder into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10min to obtain a solution b; adding the solution b into the solution a while stirring, adding an ethylene glycol solution of polyvinylpyrrolidone, continuously stirring for 30min, heating to 200 ℃, preserving heat and uniformly stirring for 12h, filtering after the reaction is finished, respectively washing three times by deionized water and absolute ethyl alcohol, and drying to obtain nano particles, wherein the dosage ratio of the nickel chloride hexahydrate to the ethylene glycol solution in the solution a is 0.65g to 35mL, and the dosage ratio of the sulfur powder to the ethylene glycol solution in the solution b is 0.152g to 35mL;
the polyethylene glycol solution of the polyvinylpyrrolidone is prepared by mixing the polyvinylpyrrolidone and the ethylene glycol according to the dosage ratio of 1.2g to 37.5mL for 10 min.
And S2, adding the prepared nano particles into an ethanol water solution with the volume fraction of 10%, adding aminopropyl trimethoxy silane, magnetically stirring, heating for reflux, and carrying out reflux reaction for 12 hours to obtain modified nano particles, wherein the weight ratio of the nano particles to the aminopropyl trimethoxy silane to the absolute ethanol is 1:1:20.
Example 2
A preparation process of a high-capacity graphite anode material comprises the following steps:
adding natural graphite and sodium nitrate into concentrated sulfuric acid, adding potassium permanganate under ice water bath, stirring at a constant speed for 1h, then adding deionized water, heating to 90 ℃, continuing stirring for 30min, then adding 30% by mass of hydrogen peroxide aqueous solution, stirring at a constant speed, reacting for 30min, centrifuging, respectively washing three times with 15% by mass of dilute hydrochloric acid and deionized water, and drying to obtain graphene sheets, wherein the dosage ratio of the natural graphite to the sodium nitrate to the concentrated sulfuric acid to the potassium permanganate to the deionized water to the hydrogen peroxide aqueous solution is 1 g:1 g:50 mL:3 g:100 mL:20 mL;
adding graphene sheets into absolute ethyl alcohol, uniformly stirring for 15min, transferring into a reaction kettle, heating to 200 ℃, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, adding modified nano particles, uniformly stirring for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h for three times to obtain gel, transferring into an ethanol aqueous solution with the volume fraction of 15% for dialysis for 6h, drying to obtain a foam precursor, sending into a tubular furnace, calcining for 2h at 550 ℃, and obtaining a graphite anode material, wherein the dosage ratio of the graphene sheets, the modified nano particles, the absolute ethyl alcohol and the soaking solution is 3 mg/0.2 mg/12 mL/150 mL.
The soaking solution is formed by mixing acetone, absolute ethyl alcohol and deionized water according to the volume ratio of 1:1:1.
The modified nanoparticle comprises the following steps:
step S1, adding nickel chloride hexahydrate into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10 minutes to obtain a solution a; adding sulfur powder into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10min to obtain a solution b; adding the solution b into the solution a while stirring, adding an ethylene glycol solution of polyvinylpyrrolidone, continuously stirring for 30min, heating to 200 ℃, preserving heat and uniformly stirring for 12h, filtering after the reaction is finished, respectively washing three times by deionized water and absolute ethyl alcohol, and drying to obtain nano particles, wherein the dosage ratio of the nickel chloride hexahydrate to the ethylene glycol solution in the solution a is 0.67g to 35.5mL, and the dosage ratio of the sulfur powder to the ethylene glycol solution in the solution b is 0.154g to 35.5mL;
the polyethylene glycol solution of the polyvinylpyrrolidone is prepared by mixing the polyvinylpyrrolidone and the ethylene glycol according to the dosage ratio of 1.2g to 37.8mL for 10 min.
And S2, adding the prepared nano particles into an ethanol water solution with the volume fraction of 10%, adding aminopropyl trimethoxy silane, magnetically stirring, heating for reflux, and carrying out reflux reaction for 12 hours to obtain modified nano particles, wherein the weight ratio of the nano particles to the aminopropyl trimethoxy silane to the absolute ethanol is 1:1.1:20.
Example 3
A preparation process of a high-capacity graphite anode material comprises the following steps:
adding natural graphite and sodium nitrate into concentrated sulfuric acid, adding potassium permanganate under ice water bath, stirring at a constant speed for 1h, then adding deionized water, heating to 90 ℃, continuing stirring for 30min, then adding 30% by mass of hydrogen peroxide aqueous solution, stirring at a constant speed, reacting for 30min, centrifuging, respectively washing three times with 15% by mass of dilute hydrochloric acid and deionized water, and drying to obtain graphene sheets, wherein the dosage ratio of the natural graphite to the sodium nitrate to the concentrated sulfuric acid to the potassium permanganate to the deionized water to the hydrogen peroxide aqueous solution is 1 g:1 g:50 mL:4 g:100 mL:20 mL;
adding graphene sheets into absolute ethyl alcohol, uniformly stirring for 15min, transferring into a reaction kettle, heating to 200 ℃, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, adding modified nano particles, uniformly stirring for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h for three times to obtain gel, transferring into an ethanol aqueous solution with the volume fraction of 15% for dialysis for 6h, drying to obtain a foam precursor, sending into a tubular furnace, calcining for 2h at 550 ℃, and obtaining a graphite anode material, wherein the dosage ratio of the graphene sheets, the modified nano particles, the absolute ethyl alcohol and the soaking solution is 4 mg/0.2 mg/18 mL/150 mL.
The soaking solution is formed by mixing acetone, absolute ethyl alcohol and deionized water according to the volume ratio of 1:1:1.
The modified nanoparticle comprises the following steps:
step S1, adding nickel chloride hexahydrate into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10 minutes to obtain a solution a; adding sulfur powder into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10min to obtain a solution b; adding the solution b into the solution a while stirring, adding an ethylene glycol solution of polyvinylpyrrolidone, continuously stirring for 30min, heating to 200 ℃, preserving heat and uniformly stirring for 12h, filtering after the reaction is finished, respectively washing three times by deionized water and absolute ethyl alcohol, and drying to obtain nano particles, wherein the dosage ratio of the nickel chloride hexahydrate to the ethylene glycol solution in the solution a is 0.68g to 37mL, and the dosage ratio of the sulfur powder to the ethylene glycol solution in the solution b is 0.156g to 37mL;
the polyethylene glycol solution of the polyvinylpyrrolidone is prepared by mixing the polyvinylpyrrolidone and the ethylene glycol according to the dosage ratio of 1.2g to 38mL for 10 min.
And S2, adding the prepared nano particles into an ethanol water solution with the volume fraction of 10%, adding aminopropyl trimethoxy silane, magnetically stirring, heating for reflux, and carrying out reflux reaction for 12 hours to obtain modified nano particles, wherein the weight ratio of the nano particles to the aminopropyl trimethoxy silane to the absolute ethanol is 1:1.2:20.
Example 4
A preparation process of a high-capacity graphite anode material comprises the following steps:
adding natural graphite and sodium nitrate into concentrated sulfuric acid, adding potassium permanganate under ice water bath, stirring at a constant speed for 1h, then adding deionized water, heating to 90 ℃, continuing stirring for 30min, then adding 30% by mass of hydrogen peroxide aqueous solution, stirring at a constant speed, reacting for 30min, centrifuging, respectively washing three times with 15% by mass of dilute hydrochloric acid and deionized water, and drying to obtain graphene sheets, wherein the dosage ratio of the natural graphite to the sodium nitrate to the concentrated sulfuric acid to the potassium permanganate to the deionized water to the hydrogen peroxide aqueous solution is 1 g:1 g:50 mL:4 g:100 mL:20 mL;
and secondly, adding the graphene sheets into absolute ethyl alcohol, uniformly stirring for 15min, transferring into a reaction kettle, heating to 200 ℃, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, adding modified nano particles, uniformly stirring for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h for three times to obtain gel, transferring into an ethanol aqueous solution with the volume fraction of 15% for dialysis for 6h, drying to obtain a foam precursor, sending into a tubular furnace, and calcining for 2h at 550 ℃ to obtain a graphite anode material, wherein the dosage ratio of the graphene sheets, the modified nano particles, the absolute ethyl alcohol and the soaking solution is 5 mg/0.3 mg/20 mL/150 mL.
The soaking solution is formed by mixing acetone, absolute ethyl alcohol and deionized water according to the volume ratio of 1:1:1.
The modified nanoparticle comprises the following steps:
step S1, adding nickel chloride hexahydrate into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10 minutes to obtain a solution a; adding sulfur powder into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10min to obtain a solution b; adding the solution b into the solution a while stirring, adding an ethylene glycol solution of polyvinylpyrrolidone, continuously stirring for 30min, heating to 200 ℃, preserving heat and uniformly stirring for 12h, filtering after the reaction is finished, respectively washing three times by deionized water and absolute ethyl alcohol, and drying to obtain nano particles, wherein the dosage ratio of the nickel chloride hexahydrate to the ethylene glycol solution in the solution a is 0.70 g:37.5 mL, and the dosage ratio of the sulfur powder to the ethylene glycol solution in the solution b is 0.158 g:37.5 mL;
the polyethylene glycol solution of the polyvinylpyrrolidone is prepared by mixing the polyvinylpyrrolidone and the ethylene glycol according to the dosage ratio of 1.4g to 38mL for 10 min.
And S2, adding the prepared nano particles into an ethanol water solution with the volume fraction of 10%, adding aminopropyl trimethoxy silane, magnetically stirring, heating for reflux, and carrying out reflux reaction for 12 hours to obtain modified nano particles, wherein the weight ratio of the nano particles to the aminopropyl trimethoxy silane to the absolute ethanol is 1:1.2:20.
Comparative example 1
In comparison with example 1, the preparation method of the nanoparticle is as follows, wherein the nanoparticle is not modified in the step S2:
adding the graphene sheet prepared in the first step into absolute ethyl alcohol, stirring at a constant speed for 15min, transferring into a reaction kettle, heating to 200 ℃, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, adding nano particles, stirring at a constant speed for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h for three times to prepare gel, transferring into an ethanol water solution with the volume fraction of 15% for dialysis for 6h, drying to prepare a foam precursor, sending into a tubular furnace, calcining at 550 ℃ for 2h to prepare a graphite anode material, and controlling the dosage ratio of the graphene sheet, the modified nano particles, the absolute ethyl alcohol and the soaking solution to be 2 mg:0.1 mg:10 mL:150 mL.
Comparative example 2
In this comparative example, compared to example 1, no modified nanoparticle was added and the preparation method was as follows:
adding the graphene sheet prepared in the first step into absolute ethyl alcohol, uniformly stirring for 15min, transferring into a reaction kettle, heating to 200 ℃, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, uniformly stirring for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h for three times to prepare gel, transferring into an ethanol aqueous solution with the volume fraction of 15% for dialysis for 6h, drying to prepare a foam precursor, sending into a tubular furnace, calcining for 2h at 550 ℃ to prepare a graphite anode material, and controlling the dosage ratio of the graphene sheet, modified nano particles, absolute ethyl alcohol and the soaking solution to be 2 mg:0.1 mg:10 mL:150 mL.
The negative electrode materials prepared in examples 1 to 4 and comparative examples 1 to 2 were assembled into button half cells, respectively, and the discharge performance of the cells was measured, and the results are shown in table 1:
TABLE 1
From the above table 1, it can be seen that examples 1 to 4 of the present invention have higher charge and discharge efficiencies and discharge capacities.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (7)
1. A preparation process of a high-capacity graphite anode material is characterized by comprising the following steps of: the method comprises the following steps:
adding natural graphite and sodium nitrate into concentrated sulfuric acid, adding potassium permanganate under ice water bath, uniformly stirring for 1h, then adding deionized water, heating to 90 ℃, continuously stirring for 30min, then adding 30% hydrogen peroxide aqueous solution by mass fraction, uniformly stirring and reacting for 30min, centrifuging, respectively washing three times with 15% dilute hydrochloric acid by mass fraction and deionized water, and drying to obtain graphene sheets;
and secondly, adding graphene sheets into absolute ethyl alcohol, uniformly stirring for 15min, transferring into a reaction kettle, heating to 200 ℃, preserving heat for 10h, cooling to room temperature, taking out, adding into a soaking solution, adding modified nano particles, uniformly stirring for 12h, filtering, adding a filter cake into deionized water, replacing the deionized water every 10h for three times to obtain gel, transferring into a 15% ethanol water solution for dialysis for 6h, drying to obtain a foam precursor, and sending into a tubular furnace to calcine for 2h at 550 ℃ to obtain the graphite anode material.
2. The process for preparing a high-capacity graphite anode material according to claim 1, wherein: the dosage ratio of the natural graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate, deionized water and aqueous hydrogen peroxide solution in the first step is controlled to be 1g to 50mL to 2-4g to 100mL to 20mL, and the dosage ratio of the graphene sheets, the modified nano particles, the absolute ethyl alcohol and the soaking solution in the second step is controlled to be 2-5mg to 0.1-0.3mg to 10-20mL to 150mL.
3. The process for preparing a high-capacity graphite anode material according to claim 1, wherein: the soaking solution is formed by mixing acetone, absolute ethyl alcohol and deionized water according to the volume ratio of 1:1:1.
4. The process for preparing a high-capacity graphite anode material according to claim 1, wherein: the modified nanoparticle comprises the following steps:
step S1, adding nickel chloride hexahydrate into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10 minutes to obtain a solution a; adding sulfur powder into a glycol solution with the volume fraction of 10%, and performing ultrasonic treatment for 10min to obtain a solution b; adding the solution b into the solution a while stirring, adding an ethylene glycol solution of polyvinylpyrrolidone, continuously stirring for 30min, heating to 200 ℃, preserving heat and uniformly stirring for 12h, filtering after the reaction is finished, respectively washing for three times by using deionized water and absolute ethyl alcohol, and drying to obtain nano particles;
and S2, adding the prepared nano particles into an ethanol water solution with the volume fraction of 10%, adding aminopropyl trimethoxy silane, magnetically stirring, heating and refluxing, and carrying out reflux reaction for 12 hours to obtain the modified nano particles.
5. The process for preparing a high-capacity graphite anode material according to claim 4, wherein: in the step S1, the dosage ratio of the nickel chloride hexahydrate to the ethylene glycol solution in the solution a is 0.65-0.70 g:35-37.5 mL, and the dosage ratio of the sulfur powder to the ethylene glycol solution in the solution b is 0.152-0.158 g:35-37.5 mL.
6. The process for preparing a high-capacity graphite anode material according to claim 4, wherein: the polyethylene glycol solution of the polyvinylpyrrolidone in the step S1 is prepared by mixing the polyvinylpyrrolidone and the ethylene glycol according to the dosage ratio of 1.2-1.4 g:37.5-38 mL for 10 min.
7. The process for preparing a high-capacity graphite anode material according to claim 4, wherein: in the step S2, the weight ratio of the nano particles, the aminopropyl trimethoxysilane and the absolute ethyl alcohol is controlled to be 1:1-1.2:20.
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