CN115744874A - Hard carbon material and preparation method and application thereof - Google Patents
Hard carbon material and preparation method and application thereof Download PDFInfo
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- CN115744874A CN115744874A CN202211706329.0A CN202211706329A CN115744874A CN 115744874 A CN115744874 A CN 115744874A CN 202211706329 A CN202211706329 A CN 202211706329A CN 115744874 A CN115744874 A CN 115744874A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 125
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000003245 coal Substances 0.000 claims abstract description 45
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 29
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- 239000002243 precursor Substances 0.000 claims abstract description 16
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- 239000012159 carrier gas Substances 0.000 claims abstract description 5
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- 239000002245 particle Substances 0.000 claims description 9
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- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003830 anthracite Substances 0.000 claims description 6
- 239000011294 coal tar pitch Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
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- 238000004519 manufacturing process Methods 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 38
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- 238000003860 storage Methods 0.000 abstract description 37
- 239000000463 material Substances 0.000 abstract description 8
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- 238000002441 X-ray diffraction Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 239000013081 microcrystal Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000005087 graphitization Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 239000002194 amorphous carbon material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007833 carbon precursor Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
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- 229910002804 graphite Inorganic materials 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- -1 Polypropylene Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
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- 239000007770 graphite material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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 provides a hard carbon material and a preparation method and application thereof, belonging to the technical field of sodium ion battery materials. The preparation method of the hard carbon material provided by the invention comprises the following steps: performing ball milling and impurity removal treatment on the coal-based material in sequence to obtain coal powder; taking inert gas as carrier gas, and carrying out gas-phase hybrid coating treatment on the coal powder by adopting a volatile carbon source to obtain a hard carbon material precursor; and carrying out high-temperature carbonization on the obtained hard carbon material precursor to obtain the hard carbon material. The hard carbon material provided by the invention is used for preparing the sodium ion battery, so that the sodium ion battery has high sodium storage capacity and first coulombic efficiency, excellent rate capability and stable long cycle performance, is far higher than the reversible sodium storage capacity of the sodium ion battery prepared from the coal-based material disclosed by the prior art, and has better application prospect.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a hard carbon material and a preparation method and application thereof.
Background
As a novel secondary battery, the sodium ion battery can be applied to various fields such as large-scale energy storage and the like due to abundant sodium resource reserves and low cost, and has a good development prospect. The negative electrode material is the key to the development of sodium ion batteries, with carbon-based materials being the most commonly used. The conventional graphite material cannot be applied to a sodium-ion battery due to small graphite interlayer and low sodium storage capacity. The amorphous carbon material has higher sodium storage capacity due to larger interlayer spacing, is nontoxic and harmless, has low cost and is easy to prepare on a large scale, and is an ideal sodium ion battery cathode material.
The amorphous carbon material mainly comprises hard carbon material and soft carbon material, wherein the hard carbon material has larger carbon layer spacing and higher amorphous degree compared with the soft carbon material, and the sodium storage capacity of the amorphous carbon material is as high as 300mAhg -1 . The coal-based material represented by anthracite, bituminous coal and lignite has high carbon content, wide resource distribution and low cost, and is an ideal amorphous carbon precursor. Hu et al prepared coal-based carbon material by directly pyrolyzing anthracite coal, and the sodium storage capacity of Hu et al reached 220mAhg -1 (EnergyStor. Mater.2016,5, 191-197). However, the material prepared by the method has limited sodium storage capacity and poor rate capability, and has larger improvement space. Thereafter, researchers used a mixture of two carbon precursors for structural manipulation. Li et al mixed chitosan and anthracite to prepare a three-dimensional porous carbon material, and the sodium storage capacity of the material reaches 283.3mAhg under the current multiplying power of 0.1C -1 (chem.electro.chem.2019, 6, 4541-4544). However, the first coulombic efficiency is low due to the porous structure, and the porous structure is difficult to be put into practical use.
Hu et al adopts a soft carbon precursor such as asphalt and petroleum coke to mix with a coal-based material and then carry out carbonization treatment, and the soft carbon precursor such as asphalt is melted and coated on the surface of coal-based pyrolytic carbon in the carbonization process (the patent publication: a method for improving the performance of a coal-based sodium ion battery cathode material and the application thereof: CN 202010141998.2), however, the carbon material treated by the method has uneven coating, too thick coating and high soft carbon occupation ratio. Moreover, the soft carbon material has larger graphitization degree and lower sodium storage capacity, so that the sodium storage capacity of the carbon material prepared by the method is only 271.4mAhg -1 . Zhang et al, which coats Pyrolytic Polypropylene (PP) on the surface of carbon material to repair pores and defect structure, can repair the specific surface of carbon materialThe area is reduced to 11.5m 2 g -1 . However, since the carbon material is directly coated by the method, the carbon crystallite structure cannot be improved, the interlayer spacing cannot be increased, and the performance cannot be further improved. Meanwhile, the specific surface after coating is still large, which indicates that the coating effect is poor, and the first effect is only 81.0% (Energy Technology,2019,7, 1900779).
Therefore, how to prepare a hard carbon material to enable a sodium ion battery prepared from the hard carbon material to have higher sodium storage capacity, first coulombic efficiency and rate capability becomes a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a hard carbon material, a preparation method and application thereof, and a sodium ion battery assembled by using the hard carbon material prepared by the preparation method provided by the invention as a negative electrode material has higher sodium storage capacity, first coulombic efficiency and rate capability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hard carbon material, which comprises the following steps:
(1) Performing ball milling and impurity removal treatment on the coal-based material in sequence to obtain coal powder;
(2) Taking inert gas as carrier gas, and carrying out gas-phase hybrid coating treatment on the pulverized coal powder obtained in the step (1) by adopting a volatile carbon source to obtain a hard carbon material precursor;
(3) And (3) carrying out high-temperature carbonization on the hard carbon material precursor obtained in the step (2) to obtain the hard carbon material.
Preferably, the coal-based material in step (1) comprises one or more of anthracite, bituminous coal and lignite.
Preferably, the particle size of the coal powder in the step (1) is 1 to 10 μm.
Preferably, the carbon source capable of being volatilized in the step (2) comprises one or more of coal pitch, coal tar and petroleum pitch.
Preferably, the mass ratio of the coal powder to the volatilizable carbon source in the step (2) is (1-20): 1.
preferably, the flow rate of the inert gas in the step (2) is 20-300 mL/min.
Preferably, the temperature of the gas phase hybrid coating treatment in the step (2) is 200-500 ℃, and the time of the gas phase hybrid coating treatment is 0.5-4 h.
Preferably, the temperature rise rate of the high-temperature carbonization in the step (3) is 2-10 ℃/min, the heat preservation temperature of the high-temperature carbonization is 600-1600 ℃, and the heat preservation time of the high-temperature carbonization is 0.5-5 h.
The invention also provides the hard carbon material prepared by the preparation method in the technical scheme.
The invention also provides application of the hard carbon material in the technical scheme in a negative electrode material of a sodium-ion battery.
The invention provides a preparation method of a hard carbon material, which comprises the following steps: performing ball milling and impurity removal treatment on the coal-based material in sequence to obtain coal powder; carrying out gas-phase hybrid coating treatment on the coal powder by adopting a volatile carbon source to obtain a hard carbon material precursor; and carrying out high-temperature carbonization on the obtained hard carbon material precursor to obtain the hard carbon material. According to the invention, the coal-based material is subjected to ball milling and impurity removal, so that the coal-based material is more uniform and dispersed, impurities in the coal-based material are reduced and even eliminated, and volatile matters of a volatile carbon source are more favorably and uniformly deposited on the surface of the coal-based material; volatile matters of a volatile carbon source are coated on the surface of the coal powder by a gas phase hybrid coating method, so that a soft carbon coating layer is formed, the coating layer effectively reduces the defects formed in the high-temperature carbonization process, reduces the specific surface area of the coal powder and increases the structural stability of the carbon material; the inert gas is taken as the carrier gas, so that volatile matters of the volatile carbon source can flow and disperse, and the thickness of the coating layer can be controlled, thereby obtaining the proper thickness of the coating layer; more importantly, in the process, hybrid crosslinking of a volatile carbon source and a coal matrix at a molecular level is realized, asphalt volatile oxygen-containing components generated by heating asphalt are crosslinked with oxygen-containing functional groups on the surfaces of coal molecules, and a hybrid microcrystal structure is formed after carbonization, so that the disorder degree of the carbon microcrystal structure in a coating layer is remarkably improved, and the distance between carbon layers is remarkably increased, thereby effectively improving the sodium storage capacity and the rate capability of the hard carbon material; in the high-temperature carbonization process, a new structure formed by crosslinking reaction can directly and effectively retain carbon, and the obtained amorphous carbon material with the hybrid microcrystal structure has high microcrystal disorder degree, lower graphitization degree and larger interlayer spacing, and is more favorable for obtaining high sodium storage capacity and rate capability by utilizing a sodium ion battery prepared from the hard carbon material.
The results of the embodiment show that the interlayer spacing of the hard carbon material provided by the invention is increased to 0.386nm; the thickness of the soft carbon coating layer of the hard carbon material is 2-15 nm, and the thickness is suitable and controllable; the sodium ion battery using the hard carbon material obtained by the preparation method as the negative electrode material has high sodium storage capacity and first coulombic efficiency, and the reversible sodium storage capacity of the sodium ion battery is up to 310mAhg -1 The first coulombic efficiency is up to more than 85%, and the capacity is up to 250mAhg under the current multiplying power of 1C -1 The rate capability is excellent, the long-circulating performance is stable, and the reversible sodium storage capacity is far higher than that of a sodium-ion battery prepared by coal-based materials disclosed by the prior art by 271.4mAhg -1 。
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of a hard carbon material prepared in example 1 of the present invention;
FIG. 2 is a BET isothermal adsorption curve and a pore size distribution curve of a hard carbon material prepared in example 1 of the present invention;
fig. 3 is an X-ray diffraction pattern (XRD) of the hard carbon material prepared in example 1 of the present invention;
fig. 4 is a High Resolution Transmission Electron Microscope (HRTEM) photograph of a hard carbon material prepared in example 1 of the present invention;
FIG. 5 is a BET isothermal adsorption curve and a pore size distribution curve of a hard carbon material prepared in comparative example 1 of the present invention;
fig. 6 is an X-ray diffraction pattern (XRD) of the hard carbon material prepared in comparative example 1 of the present invention;
fig. 7 is a high-resolution transmission electron microscope (HRTEM) photograph of a hard carbon material prepared in comparative example 1 of the present invention;
FIG. 8 is a charge-discharge curve diagram of a sodium ion battery prepared in comparative example 1 of the present invention;
fig. 9 is a graph showing the cycle performance of the sodium ion battery according to comparative example 1 of the present invention;
fig. 10 is a charge-discharge graph of a sodium ion battery prepared in application example 1 of the present invention;
fig. 11 is a graph showing the cycle performance of a sodium ion battery prepared in application example 1 according to the present invention;
fig. 12 is an X-ray diffraction pattern (XRD) of the hard carbon material prepared in example 2 of the present invention;
fig. 13 is a High Resolution Transmission Electron Microscope (HRTEM) photograph of a hard carbon material prepared in example 2 of the present invention;
fig. 14 is a charge-discharge graph of a sodium ion battery prepared in application example 2 of the present invention;
fig. 15 is a charge-discharge curve diagram of a sodium ion battery prepared in application example 3 of the present invention.
Detailed Description
The invention provides a preparation method of a hard carbon material, which comprises the following steps:
(1) Performing ball milling and impurity removal treatment on the coal-based material in sequence to obtain coal powder;
(2) Performing gas-phase hybrid coating treatment on the coal powder obtained in the step (1) by adopting a volatile carbon source to obtain a hard carbon material precursor;
(3) And (3) carrying out high-temperature carbonization on the hard carbon material precursor obtained in the step (2) to obtain the hard carbon material.
The coal-based material is subjected to ball milling and impurity removal in sequence to obtain coal powder.
In the present invention, the coal-based material preferably includes one or more of anthracite, bituminous coal, and lignite. According to the invention, by selecting the coal-based material, more organic matters in the coal-based material can be ensured, and more oxygen-containing functional groups such as carboxyl and hydroxyl are contained, so that the crosslinking reaction with a volatile carbon source is facilitated, and effective firm coating is realized.
In the invention, the rotation speed of the ball mill is preferably 300-400 r/min, more preferably 320-380 r/min, and most preferably 350r/min; the ball milling time is preferably 2 to 6 hours, more preferably 3 to 5 hours, and most preferably 4 hours; the mass ratio of the coal-based material to the ball milling beads during ball milling is preferably 1: (15 to 25), more preferably 1: (18 to 22), most preferably 1:20. according to the invention, by controlling the ball milling parameters within the range, the coal-based material can obtain a proper particle size, the particles can be dispersed more uniformly, and volatile matters of the volatile carbon source can be deposited uniformly on the surface of the particles; and the ball milling can expose active sites in the coal-based material, the reaction activity is higher, and the crosslinking reaction with volatile matters of a volatile carbon source is facilitated.
In the present invention, the impurity removal treatment preferably includes: soaking the ball-milled product in 2-4 mol/L NaOH solution for 12-24 h, performing suction filtration, soaking in 2-4 mol/L HCl solution for 12-24 h, then washing with water to neutrality, and finally drying to obtain coal powder. The invention has no special requirement on the drying operation, and the moisture in the coal powder can be fully removed by adopting the conventional drying operation in the field. According to the invention, by controlling the impurity removal process, impurities in the ball-milled product can be fully removed, so that the obtained coal powder is more favorable for carrying out a cross-linking reaction with oxygen-containing volatile components generated by a volatile carbon source, and a more disordered carbon microcrystal structure is constructed.
In the present invention, the particle size of the coal powder is preferably 1 to 10 μm, and more preferably 1 to 5 μm. The invention is more beneficial to the uniform dispersion and uniform vapor deposition of the coal powder as a volatile carbon source by controlling the particle size of the coal powder within the range.
And after the coal powder is obtained, carrying out gas-phase hybrid coating treatment on the coal powder by adopting a volatile carbon source to obtain a hard carbon material precursor.
In the present invention, the inert atmosphere preferably includes one or more of helium, argon, neon and xenon. According to the invention, volatile deposition and crosslinking reaction of the volatile carbon source are carried out in the inert gas atmosphere, so that the coal powder and the volatile carbon source can be prevented from being consumed by oxygen in the air, and impurities such as water and the like are prevented from being introduced; meanwhile, inert gas is used as a carrier of volatile matters of the volatile carbon source, the volatile matters are carried to the surface of the coal dust, and the flowing inert gas can enable the volatile matters to be more uniformly dispersed, so that the thickness of the coating layer is controllable, and the proper thickness of the coating layer is obtained.
In the present invention, the mass ratio of the coal powder to the volatilizable carbon source is preferably (1 to 20): 1, more preferably (5 to 15): 1, most preferably (5 to 10): 1. according to the invention, by controlling the mass ratio of the coal powder to the volatile carbon source, the soft carbon layer with a proper thickness can be deposited and coated on the surface of the coal powder.
In the present invention, the flow rate of the inert gas is preferably 20 to 300mL/min, more preferably 50 to 250mL/min, and most preferably 100 to 200mL/min. By controlling the flow rate of the inert gas within the range, the volatile matter of the volatile carbon source can have a proper deposition rate and be dispersed more uniformly, so that the thickness of the coating layer is controllable, and the proper thickness of the coating layer is obtained.
In the present invention, the volatilizable carbon source preferably includes one or more of coal pitch, coal tar and petroleum pitch. In the present invention, the coal pitch preferably includes one or more of low-temperature coal pitch, medium-temperature coal pitch, and high-temperature coal pitch. According to the invention, by selecting the volatile carbon source of the above kind, more oxygen-containing functional groups such as carboxyl, hydroxyl and the like can be ensured in the volatile matter of the volatile carbon source, and the volatile carbon source is more favorable for carrying out crosslinking reaction with the volatile carbon source, so that the hybrid microcrystal structure in the coating layer is constructed and effectively and firmly coated.
In the present invention, the temperature increase rate of the gas phase hybrid coating treatment is preferably 1 to 10 ℃/min, more preferably 3 to 7 ℃/min, and most preferably 5 to 6 ℃/min. According to the invention, by controlling the temperature rise rate of the gas phase hybrid coating treatment within the range, the volatile matter of the volatile carbon source can have a proper volatilization rate, so that the volatile matter can be more favorably and uniformly deposited on the surface of the coal powder to form a uniform and controllable coating layer, and crosslinking can be carried out after the temperature rises to reach the temperature of crosslinking reaction, thereby realizing the construction of a hybrid microcrystal structure in the coating layer and effective and firm coating.
In the invention, the temperature of the gas-phase hybrid coating treatment is preferably 200-500 ℃, more preferably 250-450 ℃, and most preferably 400 ℃; the time for the gas phase hybrid coating treatment is preferably 0.5 to 4 hours, more preferably 1 to 3.5 hours, most preferably 1.5 to 3 hours, and further preferably 2 to 2.5 hours. According to the invention, the temperature and time of the gas-phase hybrid coating treatment are controlled within the above range, so that the volatile matter of the volatile carbon source and the coal powder can be subjected to a crosslinking reaction, a hybrid microcrystalline structure carbon material suitable for sodium storage can be formed, the disorder degree of a microcrystalline structure in the coating layer can be improved, and the distance between carbon layers can be increased, so that the prepared sodium ion battery has high sodium storage capacity and rate capability.
In the present invention, the gas-phase hybrid cladding treatment preferably includes: and placing the volatilizable carbon source at one end of an air inlet of the tubular furnace, placing the pulverized coal powder at one end of an air outlet of the tubular furnace, introducing inert gas into the air inlet, and starting a temperature control program of the tubular furnace. By controlling the operation, the invention is more beneficial to the uniform deposition of the oxygen-containing volatile matters in the volatile carbon source on the surface of the coal dust and the crosslinking reaction.
In the present invention, the cooling means of the gas-phase hybrid coating treatment is preferably furnace cooling.
And after obtaining a hard carbon material precursor, carrying out high-temperature carbonization on the hard carbon material precursor to obtain the hard carbon material. According to the invention, oxygen-containing volatile components in the volatile carbon source and coal are subjected to a crosslinking reaction to form a stable crosslinked macromolecular structure, and the disordered carbon layer structure can be retained under high-temperature carbonization, so that a hybrid microcrystalline structure carbon material is obtained, the microcrystalline layer spacing more suitable for sodium storage is provided, and the sodium ion battery prepared from the hard carbon material has high sodium storage capacity and rate capability.
In the invention, the heating rate of the high-temperature carbonization is preferably 2-10 ℃/min, more preferably 3-7 ℃/min, and most preferably 5-6 ℃/min; the heat preservation temperature of the high-temperature carbonization is preferably 600-1600 ℃, more preferably 800-1500 ℃, and most preferably 1000-1200 ℃; the holding time for the high-temperature carbonization is preferably 0.5 to 5 hours, more preferably 1 to 4 hours, and most preferably 2 to 3 hours. According to the invention, by controlling the parameter of high-temperature carbonization within the range, redundant elements such as oxygen, nitrogen and sulfur can be removed under the condition of better retaining the carbon skeleton, so that the carbon skeleton of the hard carbon material has larger carbon spacing and lower graphitization degree, and the sodium ion battery prepared by using the hard carbon material is more beneficial to obtaining higher sodium storage capacity and rate capability.
In the present invention, the atmosphere of the high-temperature carbonization is preferably an inert gas atmosphere.
In the present invention, the cooling method for the high-temperature carbonization is preferably furnace cooling.
The hard carbon material prepared by the preparation method provided by the invention can obtain a carbon microcrystal structure with larger interlayer spacing and lower graphitization degree and a controllable coating thickness, and a sodium ion battery prepared from the hard carbon material prepared by the preparation method has higher sodium storage capacity and rate capability; and the preparation method is simple, the parameters are easy to control, and the cost is low.
The invention also provides the hard carbon material prepared by the preparation method in the technical scheme.
In the present invention, the specific surface area of the hard carbon material is preferably 1 to 10m 2 g -1 (ii) a The (002) crystal face interlayer spacing of the hard carbon material is preferably 0.37-0.39 nm; the thickness of the coating layer of the hard carbon material is preferably 2 to 15nm. According to the invention, by controlling the parameters of the hard carbon material within the above range, the sodium ion battery prepared by using the hard carbon material is more beneficial to obtaining higher sodium storage capacity and rate capability.
The invention also provides application of the hard carbon material in the technical scheme in a negative electrode material of a sodium-ion battery. The method of the present invention is not particularly limited, and the method of the present invention may be applied to a hard carbon material prepared by a method known to those skilled in the art.
The application of the hard carbon material in the cathode material of the sodium-ion battery can ensure that the sodium-ion battery has high sodium storage capacity and first coulombic efficiency, excellent rate capability and stable long cycle performance, is far higher than the reversible sodium storage capacity of the sodium-ion battery prepared by the coal-based material disclosed by the prior art, and has better application prospect.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a hard carbon material specifically comprises the following steps:
(1) Performing ball milling and impurity removal treatment on the coal-based material in sequence to obtain coal powder; the method specifically comprises the following steps: selecting lignite as a coal-based material, putting 10g of lignite into an agate ball-milling tank, wherein the mass ratio of the coal-based material to ball-milling beads is 1: 20; ball milling is carried out in a ball mill for 4 hours at the speed of 350r/min; and (3) soaking the ball-milled product in a hydrochloric acid solution with the concentration of 3mol/L for 24 hours, then carrying out suction filtration, then soaking the powder in a NaOH solution with the concentration of 3mol/L for 24 hours, then washing the powder to be neutral by deionized water, and finally drying the powder to obtain the coal powder with the particle size of 1-10 microns.
(2) Taking inert gas as carrier gas, and carrying out gas-phase hybrid coating treatment on the pulverized coal powder obtained in the step (1) by adopting a volatile carbon source to obtain a hard carbon material precursor; the method specifically comprises the following steps: selecting high-temperature coal tar pitch powder as a volatile carbon source, placing the coal tar pitch powder in a corundum boat close to an air inlet, and placing the coal tar pitch powder in a corundum boat close to an air outlet; the mass ratio of the coal powder to the coal pitch is 10: 1, and argon with the flow rate of 100mL/min is simultaneously introduced into the pipe; starting a temperature rise program of the tube furnace, firstly raising the temperature to 400 ℃ at the speed of 5 ℃/min, and then preserving the temperature for 2h to obtain the hard carbon material precursor after cooling along with the furnace.
(3) Carrying out high-temperature carbonization on the hard carbon material precursor obtained in the step (1) to obtain a hard carbon material; the method specifically comprises the following steps: heating to 1200 ℃ at the speed of 5 ℃/min by adopting programmed heating in the argon atmosphere in a tubular furnace, and then preserving heat for 2h to obtain the hard carbon material after furnace cooling.
The hard carbon material prepared in example 1 above was subjected to SEM test, and the results are shown in fig. 1.
As can be seen from fig. 1, the hard carbon material is in the form of a random particle, indicating a relatively smooth, not rich pore structure.
The hard carbon material prepared in example 1 was subjected to an isothermal nitrogen adsorption specific surface area test, and the results are shown in fig. 2.
The specific surface area of the hard carbon material calculated according to FIG. 2 was 5.95m 2 g -1 And the pore diameter distribution is mainly microporous.
The hard carbon material prepared in example 1 was subjected to X-ray diffraction spectrum test, and the results are shown in fig. 3.
According to the calculation of figure 3, the angle corresponding to the (002) peak is 23.5 degrees, and the crystal face spacing calculated according to the Bragg formula is 0.386nm, which indicates that the hard carbon material has low graphitization degree, large graphite layer spacing and sufficient sodium storage sites; and a larger interlayer spacing indicates a higher degree of disorder in the material.
The hard carbon material prepared in the above example 1 was subjected to a high resolution transmission electron microscope characterization test, and the result thereof is shown in fig. 4.
As can be seen from fig. 4, the microcrystalline structure of the hard carbon material is disordered, the coating layer part is a regular soft carbon structure, the thickness is 3.8nm, and the interlayer distance obtained by measurement is 0.387nm.
Application example 1
The powder of hard carbon material prepared in example 1 was mixed with sodium carboxymethyl cellulose in a ratio of 95:5, adding a proper amount of water, grinding to form slurry, then uniformly coating the slurry on a current collector copper foil, and drying in a drying oven in vacuum to obtain the electrode containing the hard carbon material.
Placing the electrode in a glove box under Ar atmosphere, using sodium metal as counter electrode, the electrode containing hard carbon material as working electrode, and NaClO 4 (EC + DEC +5% FEC) was assembled in the electrolyte as a CR2025 type coin cell and tested.
The hard carbon material prepared in example 1 was subjected to an isothermal nitrogen adsorption specific surface area test, and the results are shown in fig. 2.
The specific surface area of the hard carbon material calculated according to FIG. 2 was 5.95m 2 g -1 And the pore diameter distribution is mainly microporous.
The hard carbon material prepared in example 1 was subjected to X-ray diffraction spectrum test, and the results are shown in fig. 3.
According to the calculation of figure 3, the angle corresponding to the (002) peak is 23.5 degrees, and the interplanar spacing calculated according to the Bragg formula is 0.386nm, which shows that the hard carbon material has low graphitization degree, large graphite layer spacing and sufficient sodium storage sites; and a larger interlayer spacing indicates a higher degree of disorder in the material.
The hard carbon material prepared in example 1 was subjected to high resolution transmission electron microscopy characterization test, and the results are shown in fig. 4.
As can be seen from fig. 4, the microcrystalline structure of the hard carbon material is disordered, the coating layer part is a regular soft carbon structure, the thickness is 3.8nm, and the interlayer distance obtained by measurement is 0.387nm.
Comparative example 1
The lignite powder obtained in the step (1) in the example 1 is directly carbonized, and is heated to 1200 ℃ at the speed of 5 ℃/min by adopting the programmed heating in a tubular furnace, and then is kept for 2 hours to finish the high-temperature carbonization treatment, so that the hard carbon material is obtained.
The powder of hard carbon material prepared in comparative example 1 was mixed with sodium carboxymethyl cellulose in a ratio of 95:5, adding a proper amount of water as a solvent, grinding to form slurry, then uniformly coating the slurry on a current collector copper foil, and drying in a vacuum oven to obtain the electrode containing the hard carbon material.
Placing the above electrode in a glove box under Ar atmosphere, using sodium metal as counter electrode, the above electrode containing hard carbon material as working electrode, and NaClO 4 (EC + DEC +5% FEC) was assembled in the electrolyte as a CR2025 coin cell and tested.
The hard carbon material prepared in comparative example 1 above was subjected to an isothermal nitrogen adsorption specific surface area test, and the results are shown in fig. 5.
The specific surface area of the hard carbon material calculated according to FIG. 5 was 169.2m 2 g -1 The specific surface area is large.
The hard carbon material prepared in comparative example 1 was subjected to X-ray diffraction pattern test, and the results are shown in fig. 6.
According to the calculation of fig. 6, the angle corresponding to the (002) peak is 25.6 degrees, and the interplanar spacing calculated according to the bragg formula is 0.348nm, which indicates that the hard carbon material of the comparative example 1 has high degree of order, small interlayer spacing and no sufficient sodium storage sites.
The hard carbon material prepared in comparative example 1 was subjected to a high-resolution transmission electron microscope characterization test, and the results are shown in fig. 7.
As can be seen from fig. 7, the crystallite structure of the hard carbon material is regular, and the interlayer distance obtained by measurement is 0.347nm.
Performance testing
The battery prepared in comparative example 1 was subjected to a charge and discharge performance test under the following test conditions: constant current charging and discharging; the current density is 0.03Ag -1 (ii) a The discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 8 and 9.
As can be seen from the charging and discharging curves of FIG. 8, the first cycle Chu Na has a specific capacity as high as 290.2mAhg -1 The first-week coulombic efficiency was 59.9%, with a comparatively poor sodium storage capacity and a lower first-time coulombic efficiency.
As can be seen from the cyclic curve of FIG. 9, the Ag concentration is 0.05Ag -1 After 200 cycles, the capacity retention rate reaches 81.5%, and the cycle stability is poor.
The battery prepared in application example 1 was subjected to a charge and discharge performance test under the following test conditions: constant current charging and discharging; the current density is 0.03Ag -1 (ii) a The discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 10 and 11.
As can be seen from the charging and discharging curves of FIG. 10, the first cycle Chu Na has a specific capacity as high as 312.2mAhg -1 The first coulombic efficiency is 85.3%, and the sodium storage capacity is higher and the first coulombic efficiency is good.
From the cycle curves of FIG. 11, it can be seen that the Ag is 0.05Ag -1 The capacity retention rate reaches 94.5 percent after 200 cycles under the current density of (2).
Compared with the comparative example 1, the comprehensive sodium storage performance of the application example 1 is obviously improved.
Example 2
The mass ratio of the coal powder to the medium temperature coal pitch in example 1 was replaced by 5: 1, and the remaining technical characteristics were the same as those of example 1, to obtain a hard carbon material.
The hard carbon material prepared in example 2 was subjected to X-ray diffraction spectrum test, and the results are shown in fig. 12.
According to the calculation of figure 12, the angle corresponding to the (002) peak is 23.7 degrees, and the interplanar spacing calculated according to the Bragg formula is 0.383nm, which shows that the hard carbon material has low graphitization degree, large graphite layer spacing and sufficient sodium storage sites; and a larger interlayer spacing indicates a higher degree of material disorder.
The hard carbon material prepared in example 2 above was subjected to high resolution transmission electron microscopy characterization test, and the results are shown in fig. 13.
As can be seen from fig. 13, the microcrystalline structure of the hard carbon material was disordered, the coating layer portion was a regular soft carbon structure, the thickness was 5.2nm, and the interlayer distance was 0.384nm by measurement.
Application example 2
The powder of hard carbon material prepared in example 2 was mixed with sodium carboxymethyl cellulose in a ratio of 95:5, adding a proper amount of water, grinding to form slurry, and then uniformly coating the slurry on a current collector copper foil to obtain the electrode containing the hard carbon material.
Placing the electrode in a glove box under Ar atmosphere, using sodium metal as counter electrode, the electrode containing hard carbon material as working electrode, and NaClO 4 (EC + DEC +5% FEC) was assembled in the electrolyte as a CR2025 coin cell and tested.
Performance test
The battery prepared in the application example 2 was subjected to a charge and discharge performance test under the following test conditions: constant current charging and discharging; the current density is 0.03Ag -1 (ii) a The discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V, and the test results are shown in fig. 14.
The charge-discharge curve result in FIG. 14 shows that the initial reversible sodium storage specific capacity is 303.4mAhg -1 First coulombic efficiency88.2%, the capacity and first effect are significantly improved compared to comparative example 1.
Example 3
The volatilizable carbon source in the embodiment 1 is replaced by petroleum asphalt, the mass ratio of the coal powder to the volatilizable carbon source is replaced by 1:1, and the rest technical characteristics are the same as the embodiment 1, so that the hard carbon material is obtained.
Application example 3
The powder of hard charcoal material prepared in example 3 was mixed with sodium carboxymethyl cellulose in a ratio of 95:5, adding a proper amount of water, grinding to form slurry, and then uniformly coating the slurry on a current collector copper foil to obtain the electrode containing the hard carbon material.
The electrode was placed in a glove box under Ar atmosphere, and sodium metal was used as a counter electrode, the carbon material electrode was used as a working electrode, and NaClO was used as a working electrode 4 (EC + DEC +5% FEC) was assembled in the electrolyte as a CR2025 coin cell and tested.
Performance testing
The battery prepared in application example 3 was subjected to a charge and discharge performance test under the following test conditions: constant current charging and discharging; the current density is 0.03Ag -1 (ii) a The discharge cutoff voltage was 0.001V and the charge cutoff voltage was 3V. The test results are shown in fig. 15.
The charge-discharge curve results in FIG. 15 show that the first reversible sodium storage specific capacity is 301.2mAhg -1 The first coulombic efficiency was 81.8%.
It can be seen from the above examples and comparative examples that the hard carbon material provided by the invention is used for preparing a sodium ion battery, so that the sodium ion battery has high sodium storage capacity and first coulombic efficiency, excellent rate capability, stable long cycle performance, and better application prospect, and is far higher than the reversible sodium storage capacity of the sodium ion battery prepared from the coal-based material disclosed by the prior art.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method of preparing a hard carbon material, comprising the steps of:
(1) Performing ball milling and impurity removal treatment on the coal-based material in sequence to obtain coal powder;
(2) Taking inert gas as carrier gas, and carrying out gas-phase hybrid coating treatment on the pulverized coal powder obtained in the step (1) by adopting a volatile carbon source to obtain a hard carbon material precursor;
(3) And (3) carrying out high-temperature carbonization on the hard carbon material precursor obtained in the step (2) to obtain the hard carbon material.
2. The method according to claim 1, wherein the coal-based material in step (1) comprises one or more of anthracite, bituminous coal and lignite.
3. The method according to claim 1, wherein the particle size of the coal powder in the step (1) is 1 to 10 μm.
4. The method according to claim 1, wherein the carbon source capable of being volatilized in the step (2) comprises one or more of coal pitch, coal tar and petroleum pitch.
5. The production method according to claim 1, wherein the mass ratio of the coal powder to the source of volatilizable carbon in the step (2) is (1 to 20): 1.
6. the method according to claim 1, wherein the flow rate of the inert gas in the step (2) is 20 to 300mL/min.
7. The method according to claim 1, wherein the temperature of the gas phase hybrid coating treatment in the step (2) is 200 to 500 ℃ and the time of the gas phase hybrid coating treatment is 0.5 to 4 hours.
8. The preparation method according to claim 1, wherein the temperature rise rate of the high-temperature carbonization in the step (3) is 2-10 ℃/min, the holding temperature of the high-temperature carbonization is 600-1600 ℃, and the holding time of the high-temperature carbonization is 0.5-5 h.
9. A hard carbon material produced by the production method according to any one of claims 1 to 8.
10. Use of the hard carbon material of claim 9 in a sodium ion battery negative electrode material.
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