CN115744872B - Asphalt-based soft carbon composite cellulose hard carbon negative electrode material and preparation method thereof - Google Patents
Asphalt-based soft carbon composite cellulose hard carbon negative electrode material and preparation method thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 58
- 229910021384 soft carbon Inorganic materials 0.000 title claims abstract description 55
- 239000010426 asphalt Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 229920002678 cellulose Polymers 0.000 title claims abstract description 25
- 239000001913 cellulose Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007773 negative electrode material Substances 0.000 title abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 238000001816 cooling Methods 0.000 claims abstract description 33
- 238000000227 grinding Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000007833 carbon precursor Substances 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000010405 anode material Substances 0.000 claims description 16
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 15
- 244000105624 Arachis hypogaea Species 0.000 claims description 15
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 15
- 235000018262 Arachis monticola Nutrition 0.000 claims description 15
- 235000020232 peanut Nutrition 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000011267 electrode slurry Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000011229 interlayer Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 238000007605 air drying Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 241000209094 Oryza Species 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002194 amorphous carbon material Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a pitch-based soft carbon composite cellulose hard carbon negative electrode material, which comprises the steps of ultrasonically washing and drying a hard carbon material to obtain a hard carbon precursor; transferring the hard carbon precursor to a tube furnace for pre-carbonization under the air atmosphere, wherein the pre-carbonization temperature is 250-350 ℃, and grinding after the pre-carbonization is completed and naturally cooling to obtain a pre-carbonized product; uniformly mixing asphalt and a pre-carbonized product, putting the mixture into a ball milling tank, adding pure water, and then performing ball milling and full compounding to obtain a hard carbon composite asphalt-based soft carbon material precursor; and transferring the dried product into a tube furnace, and carrying out pyrolysis carbonization under the protection of inert gas. The soft and hard carbon composite material prepared by the invention has proper interlayer spacing, is favorable for intercalation and deintercalation of sodium ions, has higher first coulomb efficiency and reversible specific capacity, has good cycling stability, and is an ideal negative electrode material of sodium ion batteries.
Description
Technical Field
The invention belongs to the field of preparation of sodium ion battery electrode materials, and particularly relates to a hard carbon composite asphalt-based soft carbon negative electrode material for a sodium ion battery and a preparation method thereof.
Background
Since 2010, sodium ion battery research has entered a resumption period, and researchers have reported a variety of sodium ion battery cathode materials, anode materials, electrolyte systems, and the like. Wherein the positive electrode material mainly comprises layered and tunnel transition metal oxides, polyanion compounds, prussian blue analogues, organic materials and the like; the cathode material mainly comprises carbon materials, alloys, phosphide, organic carboxylate and the like.
In the field of carbon materials, amorphous carbon materials are generally classified into graphitizable and graphitizable carbon according to the ease of graphitization. Graphitizable carbon, also referred to as soft carbon, generally refers to carbon materials that can be graphitized above 2800 ℃ and the disordered structure is easily eliminated. Hard graphitized carbon, also known as hard carbon, generally refers to carbon that is difficult to completely graphitize at 2800 ℃ and whose disordered structure is difficult to eliminate at high temperatures. The two amorphous carbon materials differ primarily in the manner in which the carbon layers that make up them differ in arrangement.
Hard carbon materials generally exhibit good sodium storage properties, but their precursors are generally biomass or synthetic resins, which are costly and low in carbon yield, and are difficult to highlight in strong competition. Mesophase pitch (waste residue from the petroleum industry) can be used as a soft carbon precursor at lower cost, and the soft carbon produced has a more ordered structure, fewer defects and shorter interlayer spacing, but tends to have a lower specific capacity than hard carbon. Combining both can provide a good strategy for developing low cost and high performance carbon-based anode materials in view of the advantages of hard carbon and soft carbon each.
Disclosure of Invention
The invention aims to solve the technical problem of providing an asphalt-based soft carbon composite cellulose hard carbon negative electrode material and a preparation method thereof, so as to achieve the purpose of further improving the specific capacity and the first coulomb efficiency of the material.
To solve the above technical problems, according to an aspect of the present invention, there is provided a method for preparing a pitch-based soft carbon composite cellulose hard carbon anode material, comprising:
step one, performing ultrasonic washing and drying on a hard carbon material to obtain a hard carbon precursor; the hard carbon material is one or the combination of more of peanut shells, rice hulls or cellulose.
Transferring the hard carbon precursor to a tube furnace for pre-carbonization in an air atmosphere, wherein the pre-carbonization temperature is 250-350 ℃, and grinding after the pre-carbonization is completed and naturally cooling to obtain a pre-carbonized product.
Step three: asphalt and a pre-carbonized product are mixed according to the mass ratio of (9-1): 1, uniformly mixing, placing the mixture in a ball milling tank, adding pure water, and then performing ball milling and full compounding to obtain the hard carbon composite asphalt-based soft carbon material precursor.
Asphalt is a polymer mixture, has the advantages of wide sources, low price, high carbon yield and the like, is a high-quality resource for preparing carbon-based materials, and is convenient for mass production.
Step four: drying and grinding the hard carbon composite asphalt-based soft carbon material precursor to obtain black powder; the method comprises the following steps of (1) putting slurry of a hard carbon composite asphalt-based soft carbon material precursor into a drying oven at 100 ℃ for drying treatment for 12 hours; then put into a mortar for full grinding.
Step five: transferring the black powder into a tube furnace, carrying out pyrolysis carbonization under the protection of inert gas, maintaining the pyrolysis carbonization temperature at 700-900 ℃ for 7-9 hours, naturally cooling to room temperature, taking out the product, grinding and sieving.
Further, in the first step, the ultrasonic washing time is 6-12 hours, and the temperature of the cleaning liquid is 30-80 ℃.
Further, in the second step, the temperature rising rate is 5 ℃/min and the heat preservation time is 3 hours during the pre-carbonization.
Further, in the third step, the mass ratio of the asphalt to the pre-carbonized product is 9:1, 7:3 and 1:1.
Further, in the fifth step, during pyrolysis carbonization, the temperature is raised at a temperature raising rate of 5-10 ℃/min.
Further, in the fifth step, the inert gas is selected from nitrogen, argon, hydrogen-argon mixture (5%H) 2 +95 Ar).
According to another aspect of the invention, there is provided a sodium ion battery carbon negative electrode material prepared by the above method.
According to another aspect of the present invention, there is provided a soft and hard carbon composite electrode sheet, characterized in that: uniformly grinding the carbon cathode material of the sodium ion battery, acetylene black and sodium carboxymethylcellulose according to a proportion, adding ultrapure water, magnetically stirring to obtain uniformly mixed electrode slurry, uniformly coating the battery slurry on copper foil by using a coating machine, placing the copper foil in a vacuum drying oven for drying, and preparing the copper foil into a wafer electrode to obtain the soft and hard carbon composite electrode slice.
Further, the mass ratio of the carbon cathode material of the sodium ion battery to the acetylene black to the sodium carboxymethylcellulose is 7:2:1.
According to another aspect of the invention, there is provided a sodium ion battery comprising the above-described asphalt-based soft and hard carbon composite electrode sheet.
In order to improve the carbon yield of the carbon-based material and reduce the material cost, the invention takes peanut shell, rice hull and cellulose as hard carbon precursors, asphalt as soft carbon precursors, and the two are mixed according to different proportions and then carbonized and cracked to prepare the soft and hard carbon composite material, thereby effectively improving the electrochemical performance of the soft carbon anode material of the sodium ion battery, and the initial specific capacity is 208mAhg -1 To 315mAhg -1， The first effect is increased from 56% to 71%.
The method of presintering and carbonizing in a muffle furnace enables the hard carbon precursor organic carbon chain to initially form a ring structure, and simultaneously introduces an oxygen functional group; the asphalt graphitization structure can be slowly formed and generate less closed pores by pyrolysis carbonization in the tube furnace, so that irreversible capacity loss of the composite material is effectively reduced, and the prepared soft and hard carbon composite material has proper interlayer spacing, is favorable for intercalation and deintercalation of sodium ions, has higher first coulombic efficiency and reversible specific capacity, and has good cycling stability, so that the composite material is an ideal negative electrode material of a sodium ion battery.
Drawings
The XRD patterns shown in fig. 1 can be seen that the characteristic peaks of the three materials of examples 1, 2 and 3 are all around 23 ° and 43 °, corresponding to (002) and (100) diffraction crystal planes, respectively, indicating that the three materials all belong to amorphous carbon materials.
The XRD patterns shown in fig. 2 can be seen that the characteristic peaks of the materials with different composite ratios in examples 3, 4 and 5 are all around 23 ° and 43 °, and no other obvious impurity peak corresponds to (002) and (100) diffraction crystal planes, respectively.
As can be seen from the Raman diagram shown in FIG. 3, the three materials of examples 1, 2, 3, 4, 5 are at 1350cm -1 And 1580cm -1 Two obvious characteristic peaks are arranged nearby and correspond to the D peak and the G peak respectively, which shows that all three materials belong to amorphous carbon materials.
It can be seen from the long cycle chart shown in fig. 4 that the asphalt cellulose composite of example 3 exhibits good cycle stability and capacity retention.
FIG. 5 shows a graph of the rate performance for the material of example 3 over 200mAhg -1 Recovery of 40mAhg -1 93.8% of capacity, and good cycle stability.
As can be seen from the charge-discharge curves shown in FIG. 6, the asphalt cellulose equal proportion composite material of example 3 shows 315.7mAhg at a current density of 20mAhg-1 and a voltage interval of 0-3V -1 And a first coulombic efficiency of 71.46%.
The CV curve shown in FIG. 7 shows that example 3 has a pair of distinct redox peaks around 0.1V, and has good reversibility.
Detailed Description
The following examples are provided to further illustrate the claimed invention. However, examples and comparative examples are provided for the purpose of illustrating embodiments of the present invention and do not exceed the scope of the inventive subject matter, which is not limited by the examples. Unless specifically indicated otherwise, materials and reagents used in the present invention are available from commercial products in the art.
Example 1
(1) The selected rice hull material was ultrasonically washed with deionized water for 6 hours to remove dust impurities, and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) placing the dried rice hulls into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, preserving heat for 3 hours, naturally cooling along with the furnace, taking out, and crushing the pre-carbonized product into powder by a crusher for later use.
(3) Asphalt powder and rice hull powder are mixed according to the mass ratio of 1:1, mixing, placing the mixture into a ball milling tank, adding pure water, and then performing ball milling and full compounding, wherein the ball milling time is 10 hours, so as to obtain the soft and hard carbon composite asphalt-based soft carbon material precursor.
(4) And (3) placing the precursor slurry in the step (3) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then placing the dried precursor slurry into a mortar for fully grinding for 15-30 min to obtain the black powdery precursor.
(5) And (3) placing the black powdery precursor in the step (4) into a tube furnace, heating from 25 ℃ to 800 ℃ at a heating rate of 5 ℃ under the protection of inert gas argon, preserving heat for 8 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the soft and hard carbon composite anode material.
Example 2
(1) The selected peanut shells were ultrasonically washed with deionized water for 6 hours to remove dust and impurities, and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) placing the dried peanut shell powder into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, preserving heat for 3 hours, and taking out after natural cooling along with the furnace for standby.
(3) Asphalt powder and peanut shell powder are mixed according to the mass ratio of 1:1, mixing, placing the mixture into a ball milling tank, adding pure water, and then performing ball milling and full compounding, wherein the ball milling time is 10 hours, so as to obtain the soft and hard carbon composite asphalt-based soft carbon material precursor.
(4) And (3) placing the precursor slurry in the step (3) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then placing the precursor slurry into a mortar for full grinding for 15-30 min to obtain the black powdery precursor.
(5) And (3) placing the black powdery precursor in the step (4) into a tube furnace, heating from 25 ℃ to 800 ℃ at a heating rate of 5 ℃ under the protection of inert gas nitrogen, preserving heat for 8 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the soft and hard carbon composite anode material.
Example 3
(1) The selected cellulose was washed ultrasonically with deionized water for 6 hours and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) placing the dried cellulose into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, preserving heat for 3 hours, and taking out after naturally cooling along with the furnace for standby.
(3) Asphalt powder and cellulose powder are mixed according to the mass ratio of 1:1, mixing, placing the mixture into a ball milling tank, adding pure water, and then performing ball milling and full compounding, wherein the ball milling time is 10 hours, so as to obtain the soft and hard carbon composite asphalt-based soft carbon material precursor.
(4) And (3) placing the precursor slurry in the step (3) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then placing the precursor slurry into a mortar for full grinding for 15-30 min to obtain the black powdery precursor.
(5) And (3) placing the black powdery precursor in the step (4) into a tube furnace, heating from 25 ℃ to 800 ℃ at a heating rate of 5 ℃ under the protection of inert gas argon, preserving heat for 8 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the soft and hard carbon composite anode material.
Example 4
(1) The selected cellulose was washed ultrasonically with deionized water for 6 hours and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) placing the dried cellulose into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, preserving heat for 3 hours, and taking out after naturally cooling along with the furnace for standby.
(3) Mixing asphalt powder and cellulose powder according to a mass ratio of 7:3, placing the mixture into a ball milling tank, adding pure water, and performing ball milling for full compounding for 10 hours to obtain a soft and hard carbon composite asphalt-based soft carbon material precursor.
(4) And (3) placing the precursor slurry in the step (3) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then placing the precursor slurry into a mortar for full grinding for 15-30 min to obtain the black powdery precursor.
(5) And (3) placing the black powdery precursor in the step (4) into a tube furnace, heating from 25 ℃ to 900 ℃ at a heating rate of 5 ℃ under the protection of inert gas argon, preserving heat for 7 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the soft and hard carbon composite anode material.
Example 5
(1) The selected cellulose was washed ultrasonically with deionized water for 6 hours and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) placing the dried cellulose into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, preserving heat for 3 hours, and taking out after naturally cooling along with the furnace for standby.
(3) Mixing asphalt powder and cellulose powder according to a mass ratio of 9:1, placing the mixture into a ball milling tank, adding pure water, and performing ball milling for full compounding for 10 hours to obtain a soft and hard carbon composite asphalt-based soft carbon material precursor.
(4) And (3) placing the precursor slurry in the step (3) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then placing the precursor slurry into a mortar for full grinding for 15-30 min to obtain the black powdery precursor.
(5) And (3) placing the black powdery precursor in the step (4) into a tube furnace, heating from 25 ℃ to 700 ℃ at a heating rate of 5 ℃ under the protection of inert gas argon, preserving heat for 9 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the soft and hard carbon composite anode material.
Example 6
(1) The selected peanut shells were ultrasonically washed with deionized water for 6 hours to remove dust and impurities, and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) placing the dried peanut shell powder into a muffle furnace, heating from 25 ℃ to 250 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, preserving heat for 3 hours, and taking out after natural cooling along with the furnace for standby.
(3) Mixing asphalt powder and peanut shell powder according to a mass ratio of 7:3, placing the mixture into a ball milling tank, adding pure water, and performing ball milling for full compounding for 10 hours to obtain a soft and hard carbon composite asphalt-based soft carbon material precursor.
(4) And (3) placing the precursor slurry in the step (3) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then placing the precursor slurry into a mortar for full grinding for 15-30 min to obtain the black powdery precursor.
(5) And (3) placing the black powdery precursor in the step (4) into a tube furnace, heating from 25 ℃ to 900 ℃ at a heating rate of 5 ℃ under the protection of inert gas nitrogen, preserving heat for 7 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the soft and hard carbon composite anode material.
Example 7
(1) The selected peanut shells were ultrasonically washed with deionized water for 6 hours to remove dust and impurities, and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) placing the dried peanut shell powder into a muffle furnace, heating from 25 ℃ to 350 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, preserving heat for 3 hours, and taking out after natural cooling along with the furnace for later use.
(3) Mixing asphalt powder and peanut shell powder according to the mass ratio of 9:1, placing the mixture into a ball milling tank, adding pure water, and performing ball milling for full compounding for 10 hours to obtain the soft and hard carbon composite asphalt-based soft carbon material precursor.
(4) And (3) placing the precursor slurry in the step (3) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then placing the precursor slurry into a mortar for full grinding for 15-30 min to obtain the black powdery precursor.
(5) And (3) placing the black powdery precursor in the step (4) into a tube furnace, heating from 25 ℃ to 700 ℃ at a heating rate of 5 ℃ under the protection of inert gas nitrogen, preserving heat for 9 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the soft and hard carbon composite anode material.
Comparative example 1
(1) The selected cellulose was washed ultrasonically with deionized water for 6 hours and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) Asphalt powder and cellulose powder are mixed according to the mass ratio of 1:1, mixing, placing the mixture into a ball milling tank, adding pure water, and then performing ball milling and full compounding, wherein the ball milling time is 10 hours, so as to obtain the soft and hard carbon composite asphalt-based soft carbon material precursor.
(3) And (3) placing the precursor slurry in the step (2) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then placing the precursor slurry into a mortar for full grinding for 15-30 min to obtain the black powdery precursor.
(4) And (3) placing the precursor in the step (3) into a tube furnace, heating from 25 ℃ to 800 ℃ at a heating rate of 5 ℃ under the protection of inert gas argon, preserving heat for 8 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the soft and hard carbon composite anode material.
Comparative example 2
(1) The selected cellulose was washed ultrasonically with deionized water for 6 hours and the resulting product was dried in a forced air drying oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) placing the dried cellulose into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, preserving heat for 3 hours, and taking out after naturally cooling along with the furnace for standby.
(3) And (3) putting the precursor slurry in the step (2) into a drying oven at 100 ℃ for drying treatment for 12 hours, and then putting into a mortar for full grinding for 15-30 min to obtain the black powdery precursor.
(4) And (3) placing the precursor in the step (3) into a tube furnace, heating from 25 ℃ to 800 ℃ at a heating rate of 5 ℃ under the protection of inert gas argon, preserving heat for 8 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the hard carbon anode material.
Comparative example 3
And (3) placing the asphalt precursor into a tubular furnace, heating from 25 ℃ to 800 ℃ at a heating rate of 5 ℃ under the protection of inert gas argon, preserving heat for 8 hours, cooling to room temperature along with the furnace at a cooling rate of 5 ℃/min, taking out, grinding, and sieving with a 325-mesh sieve to obtain the asphalt-based soft carbon anode material.
Grinding the anode materials of the sodium ion batteries of the examples and the comparative examples, acetylene black and sodium carboxymethylcellulose uniformly according to the mass ratio of 7:2:1, adding a proper amount of ultrapure water, magnetically stirring for 12 hours to obtain uniformly mixed electrode slurry, uniformly coating the slurry on copper foil by using a coating machine, placing the copper foil in a vacuum drying oven, vacuum drying at 80 ℃ for 12 hours, and preparing the copper foil into a wafer electrode with the diameter of 12mm by using a sheet punching machine to obtain the soft and hard carbon composite electrode sheet.
The embodiment provides a half-cell of a sodium ion battery, wherein the electrode plate is used as a negative electrode, a wafer with the diameter of 12mm is obtained by cutting the electrode plate made of the composite material, the wafer is compacted on a tablet press, the battery is assembled in a glove box filled with high-purity argon according to the construction of a CR2016 standard button cell, a glass fiber (Whitman, GF/A) wafer with the diameter of 19mm is used as a diaphragm, a sodium metal plate with the diameter of 12mm and the thickness of 0.2mm is used as a counter electrode and a reference electrode, 1mol/L of sodium perchlorate/ethylene carbonate/diethyl carbonate solution is used as electrolyte, and after standing for 12 hours, the battery is subjected to charge-discharge test on a blue battery test platform by using a current density of 20 mA/g.
TABLE 1 Main parameters and electrochemical Properties of examples 1-7 and comparative examples 1-3
| Composite material | Pre-carbonization | Doping ratio | Pyrolysis temperature/time | Initial specific capacity | First coulombic efficiency | |
| Example 1 | Asphalt and rice husk | Is that | 1:1 | 800℃/8h | 261.4mAh/g | 57.95% |
| Example 2 | Asphalt and peanut powder | Is that | 1:1 | 800℃/8h | 238.2mAh/g | 62.68% |
| Example 3 | Asphalt and cellulose | Is that | 1:1 | 800℃/8h | 315.7mAh/g | 71.46% |
| Example 4 | Asphalt and cellulose | Is that | 7:3 | 900℃/7h | 296.3mAh/g | 74,34% |
| Example 5 | Asphalt and cellulose | Is that | 9:1 | 700℃/9h | 303.2mAh/g | 73.28% |
| Example 6 | Asphalt and peanut powder | Is that | 7:3 | 900℃/7h | 223.4mAh/g | 61.39% |
| Example 7 | Asphalt and peanut powder | Is that | 9:1 | 700℃/9h | 243.1mAh/g | 58.18% |
| Comparative example 1 | Asphalt and cellulose | Whether or not | 1:1 | 800℃/8h | 242.5mAh/g | 70.75% |
| Comparative example 2 | Cellulose | Is that | 1 | 800℃/8h | 275mAh/g | 72.8% |
| Comparative example 3 | Asphalt | Is that | 1 | 800℃/8 | 208mAh/g | 55.7% |
The scope of the present invention is not limited to the above embodiments, but various modifications and alterations of the present invention will become apparent to those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the asphalt-based soft carbon composite cellulose hard carbon anode material is characterized by comprising the following steps:
step one, performing ultrasonic washing and drying on a hard carbon material to obtain a hard carbon precursor; the hard carbon material is one or the combination of more of peanut shells, rice hulls or cellulose;
transferring the hard carbon precursor to a tube furnace for pre-carbonization in an air atmosphere, wherein the pre-carbonization temperature is 250-350 ℃, and grinding after natural cooling after the pre-carbonization is completed to obtain a pre-carbonized product;
step three: asphalt and a pre-carbonized product are mixed according to the mass ratio of (9-1): 1, uniformly mixing, putting the mixture into a ball milling tank, adding pure water, and then performing ball milling and full compounding to obtain a hard carbon composite asphalt-based soft carbon material precursor;
step four: drying and grinding the hard carbon composite asphalt-based soft carbon material precursor to obtain black powder;
step five: transferring the black powder into a tube furnace, carrying out pyrolysis carbonization under the protection of inert gas, maintaining the pyrolysis carbonization temperature at 700-900 ℃ for 7-9 hours, naturally cooling to room temperature, taking out the product, grinding and sieving.
2. The method of manufacture of claim 1, wherein: in the first step, the ultrasonic washing time is 6-12 hours, and the temperature of the cleaning liquid is 30-80 ℃.
3. The preparation method according to claim 1 or 2, characterized in that: in the second step, the temperature rising rate is 5 ℃/min and the heat preservation time is 3 hours during pre-carbonization.
4. A method of preparation according to claim 3, characterized in that: in the third step, the mass ratio of the asphalt to the pre-carbonized product is 9:1, 7:3 or 1:1.
5. The method according to claim 1 or 4, wherein: and fifthly, heating at a heating rate of 5-10 ℃/min during pyrolysis carbonization.
6. The method of manufacturing according to claim 5, wherein: in the fifth step, the inert gas is selected from nitrogen, argon and 5%H 2 One of the hydrogen-argon mixtures of +95% Ar.
7. A carbon cathode material of a sodium ion battery is characterized in that: obtained by the process of any one of claims 1 to 6.
8. The utility model provides a soft or hard carbon combined material electrode slice which characterized in that: uniformly grinding the carbon cathode material of the sodium ion battery, acetylene black and sodium carboxymethylcellulose according to a proportion, adding ultrapure water, magnetically stirring to obtain uniformly mixed electrode slurry, uniformly coating the battery slurry on copper foil by using a coating machine, placing the copper foil in a vacuum drying oven for drying, and preparing the copper foil into a wafer electrode to obtain the soft and hard carbon composite electrode slice.
9. The soft and hard carbon composite electrode sheet according to claim 8, wherein: the mass ratio of the carbon cathode material of the sodium ion battery, the acetylene black and the sodium carboxymethylcellulose is 7:2:1.
10. A sodium ion battery characterized by: an electrode sheet comprising the pitch-based soft and hard carbon composite material of claim 8 or 9.
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