CN115744872A - Negative electrode material of asphalt-based soft carbon composite cellulose hard carbon and preparation method thereof - Google Patents
Negative electrode material of asphalt-based soft carbon composite cellulose hard carbon and preparation method thereof Download PDFInfo
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- CN115744872A CN115744872A CN202211614381.3A CN202211614381A CN115744872A CN 115744872 A CN115744872 A CN 115744872A CN 202211614381 A CN202211614381 A CN 202211614381A CN 115744872 A CN115744872 A CN 115744872A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 24
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- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
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- 239000000843 powder Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- 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
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010903 husk Substances 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
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- 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
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- 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
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a negative electrode material of pitch-based soft carbon composite cellulose hard carbon, 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 in air atmosphere, wherein the pre-carbonization temperature is 250-350 ℃, naturally cooling and grinding after the pre-carbonization is finished to obtain a pre-carbonization product; uniformly mixing the pitch and the pre-carbonization product, placing the mixture in a ball milling tank, adding pure water, and then performing ball milling and sufficient compounding to obtain a hard carbon composite pitch-based soft carbon material precursor; transferring the dried mixture to a tubular 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 beneficial to the embedding and the separation of sodium ions, has higher first coulombic efficiency and reversible specific capacity, has good cycling stability and is an ideal sodium ion battery cathode material.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials of sodium ion batteries, 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, research on sodium ion batteries has entered the revival period, and researchers have reported a variety of positive electrode materials, negative electrode materials, electrolyte systems, and the like of sodium ion batteries in succession. Wherein, the anode material mainly comprises a layered and tunnel transition metal oxide, a polyanion compound, a Prussian blue analogue, an organic material and the like; the negative electrode 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 degree of graphitization difficulty. Graphitizable carbon is also called soft carbon, and generally refers to carbon materials that can be graphitized at 2800 ℃ or higher, and disordered structures are easily eliminated. The non-graphitizable carbon is also called hard carbon, and generally refers to carbon that is difficult to completely graphitize at 2800 ℃, and the disordered structure of the carbon is difficult to eliminate at high temperature. The two amorphous carbon materials differ primarily in the arrangement of the carbon layers that make up them.
The hard carbon material generally shows good sodium storage performance, but the precursor of the hard carbon material is generally biomass or synthetic resin, so that the hard carbon material has high cost and low carbon yield and is difficult to show the advantages in intense competition. Mesophase pitch (waste residues from the petroleum industry) can be used as a precursor of soft carbon, and is low in cost, and the prepared soft carbon has a more ordered structure, fewer defects and shorter interlayer spacing, but the specific capacity of the prepared soft carbon is often lower than that of hard carbon. Combining the hard carbon and the soft carbon may provide a good strategy for developing low cost and high performance carbon-based anode materials in view of their respective advantages.
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 further improve the specific capacity and the first coulombic efficiency of the material.
In order to solve the above technical problems, according to an aspect of the present invention, there is provided a method for preparing an anode material of an asphalt-based soft carbon composite cellulose hard carbon, comprising:
firstly, carrying out ultrasonic washing and drying on a hard carbon material to obtain a hard carbon precursor; the hard carbon material is one or a combination of more of peanut shell, rice hull and cellulose.
And step two, transferring the hard carbon precursor to a tube furnace for pre-carbonization in the air atmosphere, wherein the pre-carbonization temperature is 250-350 ℃, naturally cooling after the pre-carbonization is finished, and grinding to obtain a pre-carbonization product.
Step three: mixing asphalt and a pre-carbonization product according to the mass ratio (9-1): 1, uniformly mixing, placing in a ball milling tank, adding pure water, and fully compounding by ball milling to obtain the hard carbon composite pitch-based soft carbon material precursor.
The asphalt is a high molecular mixture, has the advantages of wide source, low price, high carbon yield and the like, is a high-quality resource for preparing the carbon-based material, and is convenient for mass production.
Step four: drying and grinding the hard carbon composite asphalt base soft carbon material precursor to obtain black powder; relatively concretely, the slurry of the hard carbon composite asphalt base soft carbon material precursor is put into a drying oven at 100 ℃ for drying treatment, and the drying time is 12 hours; then put into a mortar for fully grinding.
Step five: and transferring the black powder into a tubular furnace, carrying out pyrolysis carbonization under the protection of inert gas, keeping the temperature of the pyrolysis carbonization 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 liquid for cleaning is 30-80 ℃.
Further, in the second step, during the pre-carbonization, the temperature rise rate is 5 ℃/min, and the heat preservation time is 3 hours.
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 and carbonization, the temperature is increased at the rate of 5-10 ℃/min.
Further, in step five, the inert gas is selected from nitrogen, argon, hydrogen argon mixture (5%H) 2 +95 Ar).
According to another aspect of the invention, a sodium ion battery carbon negative electrode material is provided, which is prepared by the above method.
According to another aspect of the present invention, there is provided a soft and hard carbon composite electrode sheet, wherein: the carbon negative electrode material of the sodium-ion battery, acetylene black and sodium carboxymethyl cellulose are uniformly ground in proportion, ultrapure water is added, the mixture is magnetically stirred to obtain uniformly mixed electrode slurry, the battery slurry is uniformly coated on copper foil by a coating machine, the copper foil is placed in a vacuum drying oven for drying, and then a wafer electrode is prepared, so that the soft-hard carbon composite electrode plate is obtained.
Further, the mass ratio of the carbon negative electrode material of the sodium ion battery, the acetylene black and the sodium carboxymethyl cellulose is 7.
According to another aspect of the invention, a sodium ion battery is provided, which comprises the electrode sheet made of the asphalt-based soft and hard carbon composite material.
In order to improve the carbon yield of the carbon-based material and reduce the material cost, the invention takes the peanut shell, the rice hull and the cellulose as hard carbon precursors and takes the asphalt as soft carbon precursors, and the soft carbon precursors and the asphalt 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 negative electrode material of the sodium-ion battery, and the initial specific capacity is 208mAhg -1 Increased to 315mAhg -1， The first effect is increased from 56% to 71%.
Pre-burning and carbonizing in a muffle furnace to enable the hard carbon precursor organic carbon chain to initially form a ring structure, and introducing an oxygen radical functional group; the prepared soft and hard carbon composite material has proper interlayer spacing, is beneficial to the embedding and the separation of sodium ions, has higher first coulombic efficiency and reversible specific capacity, simultaneously has good circulation stability, and is an ideal sodium ion battery cathode material.
Drawings
The XRD patterns shown in fig. 1 can show that the characteristic peaks of the three materials of examples 1, 2 and 3 are all around 23 ° and 43 °, corresponding to the (002) and (100) diffraction crystal planes, respectively, indicating that the three materials all belong to amorphous carbon materials.
The XRD pattern shown in figure 2 shows that the characteristic peaks of the materials with different compounding ratios in three examples 3, 4 and 5 are all around 23 degrees and 43 degrees, no other obvious impurity peaks exist, and the characteristic peaks correspond to (002) diffraction crystal planes and (100) diffraction crystal planes respectively.
The Raman diagram shown in FIG. 3 shows that the three materials of examples 1, 2, 3, 4 and 5 are 1350cm in length -1 And 1580cm -1 Two obvious characteristic peaks are arranged nearby and respectively correspond to a D peak and a G peak, and the three materials belong to amorphous carbon materials.
It can be seen from the long cycle profile shown in fig. 4 that the pitch cellulose composite of example 3 exhibits good cycle stability and capacity retention.
The graph of the rate capability shown in FIG. 5 shows that the material of example 3 passed 200mAhg -1 Recovery of 40mAhg -1 93.8% of the capacity and good cycle stability.
As can be seen from the charge and 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 range of 0-3V -1 And 71.46% first coulombic efficiency.
As can be seen from the CV curve shown in FIG. 7, example 3 has a pair of distinct redox peaks around 0.1V, and has good reversibility.
Detailed Description
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
(1) The selected rice hull materials are ultrasonically washed for 6 hours by deionized water, dust impurities are removed, and the obtained product is dried for 24 hours in an air-blast drying oven at 60 ℃ to remove moisture.
(2) And (3) putting the dried rice hulls into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving the 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) Mixing asphalt powder and rice husk powder according to a mass ratio of 1:1, placing the mixture into a ball milling tank, adding pure water, and then performing ball milling for 10 hours to obtain a soft and hard carbon composite pitch-based soft carbon material precursor.
(4) And (4) drying the precursor slurry in the step (3) in an oven at 100 ℃ for 12h, and then fully grinding in a mortar for 15-30min to obtain a black powdery precursor.
(5) And (3) putting 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 by using a 325-mesh sieve to obtain the soft-hard carbon composite negative electrode material.
Example 2
(1) And ultrasonically washing the selected peanut shells for 6 hours by using deionized water, removing dust impurities, drying the obtained product in a forced air drying oven at 60 ℃ for 24 hours, and removing moisture.
(2) And (3) putting the dried peanut shell powder into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min in the air atmosphere, preserving heat for 3 hours, naturally cooling along with the furnace, and taking out for later use.
(3) Mixing asphalt powder and peanut shell powder according to the mass ratio of 1:1, mixing, placing in a ball milling tank, adding pure water, and then performing ball milling for 10h to obtain the soft and hard carbon composite pitch-based soft carbon material precursor.
(4) And (4) drying the precursor slurry in the step (3) in an oven at 100 ℃ for 12h, and then fully grinding in a mortar for 15-30min to obtain a black powdery precursor.
(5) And (3) putting 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 by using a 325-mesh sieve to obtain the soft-hard carbon composite negative electrode material.
Example 3
(1) The selected cellulose was ultrasonically washed with deionized water for 6 hours and the resulting product was dried in a forced air oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) putting the dried cellulose into a muffle furnace, heating from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min in the air atmosphere, preserving heat for 3 hours, naturally cooling along with the furnace, and taking out for later use.
(3) Mixing asphalt powder and cellulose powder according to the mass ratio of 1:1, mixing, placing in a ball milling tank, adding pure water, and then performing ball milling for 10h to obtain the soft and hard carbon composite pitch-based soft carbon material precursor.
(4) And (4) drying the precursor slurry in the step (3) in an oven at 100 ℃ for 12h, and then fully grinding in a mortar for 15-30min to obtain a black powdery precursor.
(5) And (3) putting 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 by using a 325-mesh sieve to obtain the soft-hard carbon composite negative electrode material.
Example 4
(1) The selected cellulose was ultrasonically washed with deionized water for 6 hours and the resulting product was dried in a forced air oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) putting the dried cellulose into a muffle furnace, heating the cellulose from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving the heat for 3 hours, naturally cooling the cellulose along with the furnace, and taking the cellulose out for later use.
(3) Mixing asphalt powder and cellulose powder according to a mass ratio of 7:3, placing the mixture in a ball milling tank, adding pure water, and then performing ball milling for 10 hours to obtain the soft-hard carbon composite asphalt-based soft carbon material precursor.
(4) And (4) putting the precursor slurry in the step (3) into an oven at 100 ℃ for drying treatment, wherein the drying time is 12h, and then putting the precursor slurry into a mortar for fully grinding for 15 to 30min to obtain a black powdery precursor.
(5) And (3) putting 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 by using a 325-mesh sieve to obtain the soft-hard carbon composite negative electrode material.
Example 5
(1) The selected cellulose was ultrasonically washed with deionized water for 6 hours and the resulting product was dried in a forced air oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) putting the dried cellulose into a muffle furnace, heating the cellulose from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving the heat for 3 hours, naturally cooling the cellulose along with the furnace, and taking the cellulose out for later use.
(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 then performing ball milling for 10 hours to obtain the soft-hard carbon composite asphalt-based soft carbon material precursor.
(4) And (4) drying the precursor slurry in the step (3) in an oven at 100 ℃ for 12h, and then fully grinding in a mortar for 15-30min to obtain a black powdery precursor.
(5) And (3) putting 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 by using a 325-mesh sieve to obtain the soft-hard carbon composite cathode material.
Example 6
(1) And ultrasonically washing the selected peanut shells for 6 hours by using deionized water, removing dust impurities, drying the obtained product in a forced air drying oven at 60 ℃ for 24 hours, and removing moisture.
(2) And (3) putting the dried peanut shell powder into a muffle furnace, heating from 25 ℃ to 250 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 3 hours, naturally cooling along with the furnace, and taking out for later use.
(3) Mixing asphalt powder and peanut shell powder according to a mass ratio of 7:3, placing the mixture in a ball milling tank, adding pure water, and then performing ball milling for 10 hours to obtain the soft-hard carbon composite asphalt-based soft carbon material precursor.
(4) And (4) drying the precursor slurry in the step (3) in an oven at 100 ℃ for 12h, and then fully grinding in a mortar for 15-30min to obtain a black powdery precursor.
(5) And (3) putting 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 by using a 325-mesh sieve to obtain the soft-hard carbon composite negative electrode material.
Example 7
(1) And ultrasonically washing the selected peanut shells with deionized water for 6 hours, removing dust impurities, drying the obtained product in a forced air drying oven at 60 ℃ for 24 hours, and removing moisture.
(2) And (3) putting the dried peanut shell powder into a muffle furnace, heating from 25 ℃ to 350 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving the heat for 3 hours, naturally cooling along with the furnace, and taking out for later use.
(3) Mixing asphalt powder and peanut shell powder according to a mass ratio of 9:1, placing the mixture in a ball milling tank, adding pure water, and then performing ball milling for 10 hours to fully compound the mixture to obtain the soft-hard carbon composite asphalt-based soft carbon material precursor.
(4) And (4) drying the precursor slurry in the step (3) in an oven at 100 ℃ for 12h, and then fully grinding in a mortar for 15-30min to obtain a black powdery precursor.
(5) And (3) putting 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 by using a 325-mesh sieve to obtain the soft-hard carbon composite negative electrode material.
Comparative example 1
(1) The selected cellulose was ultrasonically washed with deionized water for 6 hours and the resulting product was dried in a forced air oven at 60 ℃ for 24 hours to remove moisture.
(2) Mixing asphalt powder and cellulose powder according to a mass ratio of 1:1, mixing, placing in a ball milling tank, adding pure water, and then performing ball milling for 10h to obtain the soft and hard carbon composite pitch-based soft carbon material precursor.
(3) And (3) drying the precursor slurry in the step (2) in an oven at 100 ℃ for 12h, and then fully grinding in a mortar for 15-30min to obtain a black powdery precursor.
(4) And (3) putting 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 by using a 325-mesh sieve to obtain the soft-hard carbon composite negative electrode material.
Comparative example 2
(1) The selected cellulose was ultrasonically washed with deionized water for 6 hours and the resulting product was dried in a forced air oven at 60 ℃ for 24 hours to remove moisture.
(2) And (3) putting the dried cellulose into a muffle furnace, heating the cellulose from 25 ℃ to 300 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving the heat for 3 hours, naturally cooling the cellulose along with the furnace, and taking the cellulose out for later use.
(3) And (3) drying the precursor slurry in the step (2) in an oven at 100 ℃ for 12h, and then fully grinding in a mortar for 15-30min to obtain a black powdery precursor.
(4) And (3) putting 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 by using a 325-mesh sieve to obtain the hard carbon cathode material.
Comparative example 3
And (3) putting the pitch precursor 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 by using a 325-mesh sieve to obtain the pitch-based soft carbon negative electrode material.
Uniformly grinding the negative electrode material of the sodium-ion battery, acetylene black and sodium carboxymethylcellulose of each example and each comparative example according to the mass ratio of 7.
The embodiment provides a sodium ion battery half-cell, the electrode plate is used as a negative electrode, the composite electrode plate is cut to obtain a 12 mm-diameter wafer, the wafer is compacted on a tablet press, the battery is assembled in a glove box filled with high-purity argon according to the structure of a CR2016 standard button battery, wherein a 19 mm-diameter glass fiber (Whitman, GF/A) wafer is used as a diaphragm, a 12 mm-diameter sodium metal sheet with the thickness of 0.2mm is used as a counter electrode and a reference electrode, a 1mol/L sodium perchlorate/ethylene carbonate/diethyl carbonate solution is used as an electrolyte, and the battery is subjected to charge and discharge tests on a blue-electricity battery test platform by using a current density of 20mA/g after standing for 12 hours.
TABLE 1 main parameters and electrochemical Properties of examples 1-7 and comparative examples 1-3
| Composite material | Precarbonization | 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 | Pitch and cellulose | Is that | 1:1 | 800℃/8h | 315.7mAh/g | 71.46% |
| Example 4 | Pitch and cellulose | Is that | 7:3 | 900℃/7h | 296.3mAh/g | 74,34% |
| Example 5 | Pitch 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 | Pitch and cellulose | Whether or not | 1:1 | 800℃/8h | 242.5mAh/g | 70.75% |
| Comparative example 2 | Cellulose, process for producing the same, and process for producing the same | 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 invention is not limited to the above embodiments, and various modifications and changes may be made by those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the invention should be included in the scope of the invention.
Claims (10)
1. A preparation method of an asphalt-based soft carbon composite cellulose hard carbon negative electrode material is characterized by comprising the following steps:
firstly, carrying out ultrasonic washing and drying on a hard carbon material to obtain a hard carbon precursor; the hard carbon material is one or a combination of more of peanut shell, rice hull or cellulose;
transferring the hard carbon precursor to a tubular furnace to perform pre-carbonization in air atmosphere at the temperature of 250-350 ℃, naturally cooling after the pre-carbonization is finished, and grinding to obtain a pre-carbonization product;
step three: mixing asphalt and a pre-carbonization product according to the mass ratio (9-1): 1, uniformly mixing, placing in a ball milling tank, adding pure water, and then performing ball milling and full compounding to obtain a hard carbon composite asphalt base soft carbon material precursor;
step four: drying and grinding the hard carbon composite asphalt base soft carbon material precursor to obtain black powder;
step five: and transferring the black powder into a tubular furnace, carrying out pyrolysis carbonization under the protection of inert gas, keeping the temperature of the pyrolysis carbonization at 700-900 ℃ for 7-9 hours, naturally cooling to room temperature, taking out the product, grinding and sieving.
2. The method of claim 1, wherein: in the first step, the ultrasonic washing time is 6-12 hours, and the temperature of the liquid for cleaning is 30-80 ℃.
3. The production method according to claim 1 or 2, characterized in that: in the second step, during pre-carbonization, the heating rate is 5 ℃/min, and the heat preservation time is 3 hours.
4. The production method 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 and 1:1.
5. The production method according to claim 1 or 4, characterized in that: and step five, heating at the heating rate of 5-10 ℃/min during pyrolysis and carbonization.
6. The method of claim 5, wherein: in the fifth step, the inert gas is selected from nitrogen, argon and hydrogen-argon mixture (5%H) 2 +95 Ar).
7. A carbon negative electrode material of a sodium ion battery is characterized in that: prepared by the process of any one of claims 1 to 6.
8. The utility model provides a soft or hard carbon composite electrode slice which characterized in that: the carbon negative electrode material of the sodium-ion battery, acetylene black and sodium carboxymethyl cellulose are uniformly ground in proportion, ultrapure water is added, the mixture is magnetically stirred to obtain uniformly mixed electrode slurry, the battery slurry is uniformly coated on copper foil by a coating machine, the copper foil is placed in a vacuum drying oven for drying, and then a wafer electrode is prepared, so that the soft-hard carbon composite electrode plate is obtained.
9. The electrode sheet of soft-hard carbon composite material according to claim 8, characterized in that: the mass ratio of the sodium ion battery carbon negative electrode material to the acetylene black to the sodium carboxymethyl cellulose is 7.
10. A sodium ion battery, characterized by: an electrode sheet comprising the asphalt-based soft and hard carbon composite material according to claim 8 or 9.
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