CN117466278B - Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery - Google Patents
Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery Download PDFInfo
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- CN117466278B CN117466278B CN202311434698.3A CN202311434698A CN117466278B CN 117466278 B CN117466278 B CN 117466278B CN 202311434698 A CN202311434698 A CN 202311434698A CN 117466278 B CN117466278 B CN 117466278B
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 81
- 238000000498 ball milling Methods 0.000 title claims abstract description 57
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000012986 modification Methods 0.000 title abstract description 7
- 230000004048 modification Effects 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000010426 asphalt Substances 0.000 claims description 15
- 239000002028 Biomass Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 239000003273 ketjen black Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000006245 Carbon black Super-P Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- -1 carboter Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 4
- 239000011300 coal pitch Substances 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for ball milling modification of a hard carbon material and application of the hard carbon material in a negative electrode of a sodium ion battery, and belongs to the technical field of negative electrode materials of sodium ion batteries. Ball milling is carried out on the hard carbon to obtain ball-milling modified hard carbon material, wherein the ball mass ratio is (5-1): 1, the ball milling time is 5-60min, and the ball milling rotating speed is 2000-5000r/min. According to the invention, the pore structure is regulated and controlled by adjusting the ball material ratio and the ball milling intensity, so that the hard carbon negative electrode for the sodium ion battery with different platform capacity ratios (capacity below 0.2V) is obtained. The method for ball milling and modifying the hard carbon material provided by the invention is helpful for promoting the commercial application of the hard carbon in sodium ion batteries.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery electrode negative electrode materials, and relates to a ball milling modification method of a hard carbon material and application of the ball milling modification method in a sodium ion battery negative electrode.
Background
In the background of increasingly prominent global energy and environmental problems, the development of clean energy and sustainable energy has received widespread attention in countries around the world. Battery technology and applications have evolved rapidly as the demand for renewable energy sources and related large-scale energy storage systems to replace traditional fossil fuels continues to increase. In particular, lithium ion batteries with high energy and power density, high voltage, long life, and pollution-free operation options are rapidly leading to markets, and are widely used in portable electronic devices, hybrid vehicles, and electric vehicles. However, rapid depletion of lithium resources has forced us to find other alternative metals as energy storage resources for the next generation, especially in the face of large-scale energy storage systems. The sodium ion battery has the advantages of better power characteristic, wide temperature range adaptability, excellent safety performance and the like, and has similar physical and chemical properties and higher crust reserve as lithium ions, so the sodium ion battery is expected to be a substitute of the lithium ion battery.
The carbonaceous negative electrode has excellent physicochemical properties such as electrolyte corrosion resistance, high conductivity, high specific surface area, and the like, and is certainly one of the most studied negative electrode materials at present. The preparation of hard carbon using various precursors has been reported to have excellent reversible storage capacity for sodium ions and stable cycle performance. Hard carbon is mainly sodium-stored by adsorption-intercalation and nanopore filling, and the adsorption sodium-stored slope area corresponding to a charge-discharge curve is a high-voltage area, usually more than 0.2V, while the intercalation and nanopore filling sodium-stored area is a low-voltage platform area, less than 0.2V, and proper interlayer spacing and nanopore structure are key for ensuring the capacity of the low-voltage platform. Carbonization temperature and carbonization strength are the main means of regulating the interlayer spacing and nanopores of carbon materials, but the carbonization process is often difficult to control.
Disclosure of Invention
Aiming at the problem that the pore structure of the hard carbon material is not easy to regulate and control, the invention provides a hard carbon negative electrode for sodium ion batteries, which is prepared by modifying the hard carbon material in a ball milling way and regulating and controlling the nano pore structure.
The invention provides a method for ball milling modification of a hard carbon material and application of the hard carbon material in a sodium ion battery negative electrode, wherein the hard carbon material is used as a raw material, and a pore structure is regulated and controlled by adjusting ball material ratio and ball milling strength to obtain the sodium ion battery hard carbon negative electrode with different platform capacity ratios (capacity below 0.2V). The hard carbon modification method provided by the invention is helpful for promoting the commercial application of the hard carbon in sodium ion batteries.
The invention provides the following technical scheme:
a ball milling method for modifying hard carbon material comprises ball milling hard carbon to obtain ball material with mass ratio of (5-1) 1, ball milling time of 5-60min; the ball milling rotating speed is 2000-5000r/min.
Further, the mass ratio of the ball materials is (3.5-1.5): 1, and the ball milling time is 6-40min; the ball milling rotating speed is 2800-3500r/min.
Further, wet ball milling is adopted to ball mill hard carbon, namely methanol, ethanol, glycol or glycerol are added in the ball milling process, and micromolecular alcohols can have intercalation function under high-energy ball milling, so that the distance between surface layers is enlarged, and the low-voltage intercalation capacity of the hard carbon is improved.
Further, the hard carbon is one of pitch hard carbon, biomass hard carbon and resin-based hard carbon.
Further, the preparation of the asphalt hard carbon is to prepare the hard carbon by taking coal asphalt, petroleum asphalt, natural asphalt or pre-oxidized asphalt as raw materials.
Further, the preparation of the biomass hard carbon is to carbonize the cellulose biomass as a raw material to obtain the hard carbon.
Further, the preparation method of the asphalt hard carbon comprises the steps of mixing asphalt with conductive carbon, and carbonizing at high temperature.
Further, the conductive carbon is one or more of ketjen black, super-P, acetylene black, cabot, carbon nano tube, graphene and conductive graphite.
Further, the mass ratio of the asphalt to the conductive carbon is 1 (0.05-0.3).
Further, the carbonization temperature is 700-1800 ℃.
The invention also provides application of the hard carbon material prepared by the method in the negative electrode of the sodium ion battery. The asphalt-based hard carbon is used as a negative electrode of a sodium ion battery, and the capacity of the low-potential platform is 10% -60%.
The method has the beneficial effects that the hard carbon with different low potential platform duty ratios is prepared by simple ball milling modification. When applied to the negative electrode of the sodium ion battery, the lithium ion battery has ideal low potential platform capacity.
Compared with the prior art, the invention has the following advantages:
(1) Suitable pore structure
The pore structure of the hard carbon can be adjusted through different ball-material ratios, ball milling time and rotating speeds, so that the intercalation/deintercalation of sodium ions is facilitated.
(2) Low potential platform duty cycle is adjustable
The hard carbon is ground through adjustment of different ball material ratios, ball milling time and rotating speed, and the capacity ratio of a low-potential platform of the hard carbon can be adjusted when the hard carbon is applied to the negative electrode of the sodium ion battery, so that the commercial application of the hard carbon in the sodium ion battery is facilitated and realized.
(3) Simple process and can be industrially produced
The ball milling method provided by the invention is simple in operation and has the potential of realizing batch production.
Drawings
FIG. 1 is a scanning electron microscope (a) and electrochemical test data (b) of example 1.
FIG. 2 is a scanning electron microscope (a) and electrochemical test data (b) of example 2.
FIG. 3 is a scanning electron microscope image (a) and electrochemical test data (b) of example 3.
Fig. 4 is electrochemical test data of example 4.
Fig. 5 is electrochemical test data of comparative example 1.
Detailed Description
Example 1
(1) Preparing and ball milling coal pitch-based hard carbon: grinding 0.1g Keqin black; then 1g coal pitch is ground and dissolved in 30mL methylene dichloride, and is evenly dispersed and mixed with the ground ketjen black, and the methylene dichloride is removed by drying to obtain a mixture of pitch and ketjen black; under argon atmosphere, placing the mixture of asphalt and ketjen black into a tube furnace for heating, wherein the heating program is that the temperature is 5 ℃/min to 200 ℃, and the mixture stays for 2 hours; heating to 1400 ℃ at 5 ℃/min, and staying for 2 hours; obtaining coal pitch-based hard carbon after cooling to room temperature, adding ethanol into the coal pitch-based hard carbon, wherein the mass ratio of the ball materials is 2:1, ball milling for 15min at the rotating speed of 3000r/min to obtain the asphalt-based hard carbon sodium ion battery anode material ball-milled for 15 min.
(2) Sodium ion assembly and performance testing: 0.45g of the prepared pitch carbon and 0.05g of binder (CMC, LA 133) slurry are weighed and evenly coated on a copper foil, and the punched sheet is taken out after vacuum drying for 12 hours at 80 ℃. In a glove box protected by high-purity argon, the prepared electrode and a metal sodium sheet are used as counter electrodes, a glass fiber diaphragm is used, an electrolyte solvent is NaPF 6 ester electrolyte, and no other additive is added, so that the LIR2032 button cell is assembled. The electrochemical sodium storage performance test is carried out at room temperature, and the voltage is in the range of 0-3V. Fig. 1a is a scanning electron microscope image of a sample, clearly shows the morphology of the sample, fig. 1b is a charge-discharge curve of the sample at a current density of 0.02A g -1, the discharge curve comprises a slope area and a platform area, the typical hard carbon sodium storage behavior is that the first discharge specific capacity is 247mAhg -1, and the discharge platform capacity below 0.2V is about 56% of the total capacity.
Example 2
(1) Preparing and ball milling biomass hard carbon: adding microcrystalline cellulose into ethanol, ball milling for 2 hours at 400r/min, and drying to remove the ethanol; under argon atmosphere, placing the ball-milled cellulose into a tube furnace for heating, wherein the heating program is that the temperature is 5 ℃/min and the temperature is increased to 200 ℃, and the cellulose stays for 2 hours; heating to 1400 ℃ at a speed of 5 ℃/min, staying for 2 hours, and cooling to room temperature to obtain biomass hard carbon; adding biomass hard carbon into ethanol, wherein the mass ratio of the ball materials is 2:1, ball milling for 15min at the rotating speed of 3000r/min to obtain the biomass-based hard carbon sodium ion battery anode material ball-milled for 15 min.
(2) Sodium ion assembly and performance testing: 0.40g of the hard carbon prepared above, 0.05g of acetylene black and 0.05g of binder (CMC, LA 133) slurry were weighed and uniformly coated on a copper foil, and the punched sheet was taken out after vacuum drying at 80 ℃ for 12 hours. In a glove box protected by high-purity argon, the prepared electrode and a metal sodium sheet are used as counter electrodes, a glass fiber diaphragm is used, an electrolyte solvent is NaPF 6 ester electrolyte, and no other additive is added, so that the LIR2032 button cell is assembled. The electrochemical sodium storage performance test is carried out at room temperature, and the voltage is in the range of 0-3V. Fig. 2a is a scanning electron microscope image of a sample, clearly shows the structure of the sample, and fig. 2b is a charge-discharge curve of the sample at a current density of 0.02A g -1, and a specific capacity of initial discharge of 308mAhg -1, wherein a discharge plateau capacity of less than 0.2V is about 59% of the total capacity.
Example 3
(1) Preparing and ball milling resin-based hard carbon: under argon atmosphere, placing the phenolic resin into a tube furnace for heating, wherein the heating program is that the temperature is 5 ℃/min to 200 ℃, and the phenolic resin stays for 2 hours; heating to 1400 ℃ at 5 ℃/min, and staying for 2 hours; after cooling to room temperature, adding ethanol into resin-based hard carbon, wherein the mass ratio of the ball materials is 2:1, ball milling for 15min at the rotating speed of 3000r/min to obtain the asphalt-based hard carbon sodium ion battery anode material ball-milled for 15 min.
(2) Sodium ion assembly and performance testing: 0.40g of the hard carbon prepared above, 0.05g of acetylene black and 0.05g of binder (CMC, LA 133) slurry were weighed and uniformly coated on a copper foil, and the punched sheet was taken out after vacuum drying at 80 ℃ for 12 hours. In a glove box protected by high-purity argon, the prepared electrode and a metal sodium sheet are used as counter electrodes, a glass fiber diaphragm is used, an electrolyte solvent is NaPF 6 ester electrolyte, and no other additive is added, so that the LIR2032 button cell is assembled. The electrochemical sodium storage performance test is carried out at room temperature, and the voltage is in the range of 0-3V. Fig. 3a is a scanning electron microscope image of a sample, clearly shows the morphology of the sample, and fig. 3b is a charge-discharge curve of the sample at a current density of 0.02A g -1, and a specific capacity of initial discharge of 346mAhg -1, wherein a discharge plateau capacity of less than 0.2V is about 48% of the total capacity.
Example 4
The time of the hard carbon ball milling was adjusted to 6min as in example 1. Fig. 4 is a graph of sample charge and discharge at a current density of 0.02A g -1, a specific capacity for the first discharge of 200mAhg -1, where a plateau capacity of less than 0.2V is about 42% of the total capacity.
Example 5
The time of the hard carbon ball milling was adjusted to 24min as in example 1. The sample has a specific initial discharge capacity of 267mAhg -1 at a current density of 0.02A g -1, where the plateau discharge capacity below 0.2V is approximately 31% of the total capacity.
Example 6
The time of the hard carbon ball milling was adjusted to 6min as in example 2. The sample has a specific first discharge capacity of 280mAhg -1 at a current density of 0.02A g -1, where the plateau capacity of 0.2V or less is approximately 48% of the total capacity.
Example 7
The time of the hard carbon ball milling was adjusted to 24min as in example 2. Fig. 4 is a graph of sample charge and discharge at a current density of 0.02A g -1, a first discharge specific capacity of 354mAhg -1, where the discharge plateau capacity below 0.2V is approximately 42% of the total capacity.
Example 8
The time of the hard carbon ball milling was adjusted to 24min as in example 3. The sample has a specific initial discharge capacity of 396mAhg -1 at a current density of 0.02A g -1, where the plateau discharge capacity below 0.2V is approximately 26% of the total capacity.
Example 9
As in example 1, but without the addition of ethanol during hard carbon ball milling. The sample has a specific first discharge capacity of 221mAhg -1 at a current density of 0.02A g -1, where the plateau capacity of discharge below 0.2V is approximately 50% of the total capacity.
Example 10
As in example 2, but without the addition of ethanol during hard carbon ball milling. The sample has a specific first discharge capacity of 294mAhg -1 at a current density of 0.02A g -1, where the plateau capacity of 0.2V or less is approximately 52% of the total capacity.
Comparative example 1
The resulting hard carbon was assembled and tested on batteries as in example 2, but without ball milling. Fig. 5 is a charge-discharge curve of a sample at a current density of 0.02A g -1, a specific capacity for initial discharge of 253mAhg -1, where a plateau capacity for discharge below 0.2V is approximately 37% of the total capacity.
Claims (8)
1. A method for ball milling modified hard carbon material is characterized in that: ball milling is carried out on hard carbon to obtain the ball material with the mass ratio of (5-1) of 1, the ball milling time of 5-60 min and the ball milling rotating speed of 2000-5000 r/min; wet ball milling of hard carbon is adopted, i.e. methanol, ethanol, glycol or glycerol are added in the ball milling process.
2. The method for ball milling and modifying hard carbon material according to claim 1, wherein the method comprises the following steps: the ball material mass ratio is (3.5-1.5) 1, and the ball milling time is 6-40 min; the ball milling rotating speed is 2800-3500 r/min.
3. The method for ball milling and modifying hard carbon material according to claim 1, wherein the method comprises the following steps: the hard carbon is one of pitch hard carbon, biomass hard carbon and resin-based hard carbon.
4. A method of ball milling a modified hard carbon material as claimed in claim 3, wherein: the preparation method of the asphalt hard carbon comprises the steps of mixing asphalt with conductive carbon and carbonizing at high temperature.
5. The method for ball milling and modifying hard carbon material according to claim 4, wherein the method comprises the following steps: the conductive carbon is one or more of ketjen black, super-P, acetylene black, carboter, carbon nano tube, graphene and conductive graphite.
6. The method for ball milling and modifying hard carbon material according to claim 4, wherein the method comprises the following steps: the mass ratio of the asphalt to the conductive carbon is 1 (0.05-0.3).
7. The method for ball milling and modifying hard carbon material according to claim 4, wherein the method comprises the following steps: the carbonization temperature is 700-1800 ℃.
8. Use of the hard carbon material prepared by the method of claim 1 in a negative electrode of a sodium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311434698.3A CN117466278B (en) | 2023-11-01 | 2023-11-01 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311434698.3A CN117466278B (en) | 2023-11-01 | 2023-11-01 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
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| Publication Number | Publication Date |
|---|---|
| CN117466278A CN117466278A (en) | 2024-01-30 |
| CN117466278B true CN117466278B (en) | 2024-05-17 |
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