CN115535996A - Asphalt-based hard carbon with specific microcrystalline structure and preparation method and application thereof - Google Patents
Asphalt-based hard carbon with specific microcrystalline structure and preparation method and application thereof Download PDFInfo
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- CN115535996A CN115535996A CN202211153949.6A CN202211153949A CN115535996A CN 115535996 A CN115535996 A CN 115535996A CN 202211153949 A CN202211153949 A CN 202211153949A CN 115535996 A CN115535996 A CN 115535996A
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- 239000010426 asphalt Substances 0.000 title claims abstract description 124
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 24
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 238000004458 analytical method Methods 0.000 claims abstract description 8
- 239000013081 microcrystal Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000008065 acid anhydrides Chemical group 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- RUGISKODRCWQNE-UHFFFAOYSA-N 2-(2-methylphenyl)ethanol Chemical compound CC1=CC=CC=C1CCO RUGISKODRCWQNE-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 25
- 239000010410 layer Substances 0.000 description 23
- 239000011295 pitch Substances 0.000 description 17
- 230000001276 controlling effect Effects 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 201000004569 Blindness Diseases 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011294 coal tar pitch Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011301 petroleum pitch Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 discloses asphalt-based hard carbon with a specific microcrystalline structure and a preparation method and application thereof, and relates to the field of new energy sodium ion secondary battery energy storage devices. The method comprises the following steps: firstly, screening an asphalt raw material through softening point measurement and four-component analysis; then, putting the asphalt raw material into a muffle furnace, carrying out pre-oxidation crosslinking treatment in the atmosphere of oxygen, and quantitatively introducing oxygen-containing functional groups through the regulation and control of pre-oxidation temperature and time to obtain differential crosslinking asphalt; and then transferring the differential cross-linked asphalt into a carbonization furnace, and carrying out carbonization treatment under the protection of inert gas to prepare the asphalt-based hard carbon with a specific microcrystalline structure. The invention utilizes the temperature to regulate and control the pre-oxidation crosslinking process so as to increase the proportion of specific oxygen-containing functional groups, and further regulates and controls the dehydrogenation cracking and carbonization reactions of the oxidized asphalt in the pyrolysis process through the specific oxygen-containing functional groups, thereby realizing the optimization of the asphalt-based hard carbon microcrystal structure, obtaining differentiated hard carbon materials and being applicable to different alkali metal battery systems.
Description
Technical Field
The invention relates to the field of energy storage devices of new energy sodium ion secondary batteries, in particular to a preparation method of asphalt-based hard carbon with a specific microcrystalline structure and application of the asphalt-based hard carbon to a negative electrode of a sodium ion battery.
Background
With the evolution of energy structures from traditional fossil fuels to renewable energy, the layout of the new energy industry chain is further accelerated. Under the background of 'double carbon', the key position of the energy storage technology in the energy conversion and storage system of China is more prominent, so that the demand of the lithium ion battery is driven to increase rapidly. However, the shortage of lithium resources is insufficient to support the application of lithium in the field of large-scale energy storage. In contrast, sodium is high in the crust and is chemically similar to lithium. Therefore, the sodium ion battery is expected to be applied in the field of large-scale energy storage and becomes a good supplement for the lithium ion battery.
In the energy storage system of the sodium ion battery, hard carbon with nano holes, defects and larger interlayer distance is considered to be one of the most ideal negative electrode materials of the sodium ion battery. The disordered carbon layer structure and rich edges provide a large number of active sites for the storage of sodium ions. The common precursor of the hard carbon is mainly biomass represented by starch and lignin; polymers represented by phenol resin and polyacrylonitrile; fossil-based precursors represented by coal and petroleum pitch. Among a plurality of precursors, the petroleum asphalt is mainly of an aromatic condensed ring structure, the carbon content of the petroleum asphalt is about 90 percent, and the petroleum asphalt is used as a precursor of hard carbon, so that the yield is high, and the conductivity is good; the key petroleum asphalt is a byproduct of petroleum in the production process, and the development and utilization of the energy conversion are realized at the grade of the energy conversion, so that the excess asphalt production capacity of the traditional fossil energy can be favorably accepted and digested, and the high added value utilization of the asphalt can be realized; and the development of the traditional energy to new energy is promoted.
Since pitch is a soft carbon precursor, the development of a polymerization crosslinking process is crucial for the preparation of pitch-based hard carbons. Yaxiang Lu et al formed a network cross-linked structure between coal tar pitch molecules by air pre-oxidation treatment, formed hard carbon with disordered carbon layer arrangement, and made the sodium ion battery have about one time more platform capacity, and also explored the influence of different oxidation temperature, time, carbonization temperature on electrochemical performance (Advanced Energy Materials,2018,8 (17): 1614-6840). Nour Daher et al also explored the effect of atmosphere and oxidation time on electrochemical performance by petroleum pitch (ACS appl. Energy mater.2020,3 (7), 6501-6510). Patent (201710880097.3) proposes that coal tar pitch is used as a precursor, a reticular cross-linked structure is formed among coal tar pitch molecules through air pre-oxidation treatment, hard carbon with disordered carbon layer arrangement is formed through carbonization, and the reversible specific capacity of 301.2mAh/g is obtained when the hard carbon is applied to a sodium ion battery cathode. Patent (201610459292.4) proposes that medium temperature pitch is used as a precursor, and a hard carbon material is prepared through chemical crosslinking, and can be applied to a sodium ion battery. The patent (201910543795.3) utilizes the water solubility of sulfonated asphalt, which is dissolved in water and then the pH is adjusted to achieve sufficient crosslinking of the sulfonated asphalt.
Among the various crosslinking modes, the air/oxygen crosslinking mode is directly adopted, so that the method has low cost, simple process, no impurity introduced and excellent electrochemical performance, and is the most economic crosslinking mode at present. However, the ionic radius, the ion redox potential and the ion mobility of different alkali metal batteries are different, and thus the requirements for the microstructure of hard carbon are also different. Although the method for preparing the asphalt-based hard carbon by pre-oxidation carbonization has been reported, a selective regulation method of an asphalt-based hard carbon material with a specific microcrystalline structure is still lacked aiming at different alkali metal battery systems. Research shows that the structure of the precursor is preserved after carbonization, and the microstructure of the hard carbon can be regulated and controlled by regulating the shape and the structure of the precursor. Meanwhile, at present, no report on how to select the asphalt raw material to prepare hard carbon exists, and blindness exists in the selection of the raw material asphalt.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides asphalt-based hard carbon with a specific microcrystalline structure and a preparation method and application thereof, aiming at eliminating the blindness in the selection of raw materials and the preparation process of hard carbon and realizing the purpose of obtaining a hard carbon material meeting the structural requirements by starting from requirements and through simple regulation and control means. According to the invention, the generation of oxygen-containing functional groups in the asphalt in the crosslinking process is controlled by regulating and controlling the temperature and time of oxidative crosslinking, and the structural evolution of the asphalt-based hard carbon in the pyrolysis forming process is regulated and controlled, so that the purpose of preparing the hard carbon with a specific microcrystalline structure is achieved, a basis is provided for the subsequent preparation of the asphalt-based hard carbon suitable for various application scenes, and the development and utilization of high added value of petroleum asphalt are realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a specific microcrystalline structure pitch-based hard carbon having La (carbon layer size) < 3.5nm and Lc (carbon layer stacked thickness) < 1nm; charring the cross-linked asphalt oxidized at 200-300 deg.C to obtain hard carbon with long-range disordered short-range ordered microcrystal structure, d 002 (the distance between carbon layers) is between 0.37 and 0.385 nm; charring the cross-linked asphalt oxidized at 300-400 deg.C to obtain hard carbon with completely disordered stacked microcrystal structure, d 002 (carbon layer spacing) is between 0.38 and 0.395 nm.
A preparation method of asphalt-based hard carbon with a specific microcrystalline structure comprises the following steps:
(1) Crushing, grinding and sieving raw material asphalt to obtain an asphalt raw material with the particle size of less than or equal to 20 mu m;
(2) The asphalt raw material in the step (1) is subjected to softening point determination and four-component analysis, and then an asphalt precursor is screened out;
(3) Placing the screened asphalt precursor in a muffle furnace, carrying out pre-oxidation treatment in an oxygen-containing atmosphere, carrying out oxidation crosslinking for 6-12 h, and cooling to obtain differential crosslinked asphalt with oxygen-containing functional groups in different proportions;
(4) Transferring the differential cross-linked asphalt into a tubular furnace, carbonizing for 1-10 h under inert protective atmosphere, cooling to room temperature, washing, filtering and demagnetizing the carbonized hard carbon material to finally obtain the asphalt-based hard carbon material with the specific microcrystalline structure.
Further, the method for measuring the softening point in the step (2) is that the asphalt raw material is placed in a special test tube, and is heated at a stable heating rate in the nitrogen atmosphere, a steel needle bar with the diameter of 1mm is continuously used for pricking the asphalt in the process, and when the asphalt becomes soft and starts to adhere to the steel needle, the temperature at the moment is recorded, namely the softening point of the asphalt; dissolving and separating asphaltene by using n-heptane, adsorbing the asphaltene on an alumina color column, developing and washing by using n-heptane, toluene and toluene-ethanol in sequence to obtain saturated components, aromatic components and colloid in sequence; the pitch precursor needs to satisfy: the softening point is more than or equal to 200 ℃.
Further, the oxygen-containing atmosphere in the step (3) is air, pure oxygen or ozone, and the gas flow rate is 50-300 mL/min.
Further, in the step (3), the pre-oxidation temperature is 200-400 ℃, and the heating rate is 1-5 ℃/min.
Furthermore, the oxygen-containing functional groups with different proportions in the step (3) are one or more of acid anhydride, ester group, ether bond or ketone; wherein, the oxidative crosslinking at 200-300 ℃ mainly generates ether bonds; oxidizing and crosslinking at 300-400 deg.c to produce ester radical and acid anhydride as main component.
Further, the inert protective atmosphere in the step (4) is argon or nitrogen, and the gas flow rate is 80-120 mL/min.
Furthermore, the carbonization temperature in the step (4) is 900-1600 ℃, and the temperature rise rate is 1-10 ℃/min.
Further, the washing in the step (4) is washing with acid liquor, absolute ethyl alcohol and water in sequence; wherein the acid solution is selected from one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid, and the concentration of the acid solution is 0.5-3 mol/L; the temperature of the demagnetizing process is controlled to be 50-70 ℃.
The asphalt-based hard carbon with the specific microcrystalline structure can be used for the negative electrodes of sodium ion batteries and can also be used for the negative electrodes of lithium ion batteries and potassium ion batteries.
Compared with the prior art, the invention has the following advantages:
1. the invention provides reference for the asphalt oxidation crosslinking process, and avoids the blindness of the material selection and oxidation crosslinking process.
2. The invention utilizes the temperature to regulate and control the pre-oxidation crosslinking process so as to increase the proportion of specific oxygen-containing functional groups, and further regulates and controls the dehydrogenation cracking and carbonization reactions of the oxidized asphalt in the pyrolysis process through the specific oxygen-containing functional groups, thereby realizing the optimization of the asphalt-based hard carbon microcrystal structure, obtaining differentiated hard carbon materials and being applicable to different alkali metal battery systems.
3. The technology for improving the structure of the asphalt-based hard carbon microcrystal through crosslinking provided by the invention has the advantages of simple process and obvious effect, and is expected to realize the breakthrough of the capacity and the first effect of the asphalt-based hard carbon. In addition, the invention adopts the byproduct petroleum asphalt in the petrochemical production process as the raw material, improves the electrochemical performance of the direct carbonization of the raw material through simple oxygen crosslinking, and realizes the high added value utilization of the petroleum asphalt.
Drawings
FIG. 1 is cross-linked asphalt solid nuclear magnetic resonance of example 1 of the present invention 13 C NMR photographs;
FIG. 2 is a TEM photograph of pitch-based hard carbon of example 1 of the present invention;
FIG. 3 is cross-linked asphalt solid nuclear magnetic resonance in example 2 of the present invention 13 C NMR photographs;
FIG. 4 is a TEM photograph of a pitch-based hard carbon of example 2 of the present invention;
fig. 5 is a first charge-discharge curve of the pitch-based hard carbon negative electrode in example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope to these examples. Other variations and modifications which may occur to those skilled in the art without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.
Example 1
(1) Crushing, grinding and sieving raw material asphalt to obtain an asphalt raw material with the particle size of 18 mu m;
(2) The ground and screened asphalt raw material is subjected to softening point determination and four-component analysis, and then screened to be used as a precursor with the softening point of 250 ℃;
(3) Subjecting the screened pitch precursorPlacing the body in a muffle furnace, and under the oxygen atmosphere, controlling the oxygen flow rate to be 150mL/min; heating from room temperature to 250 deg.C, heating at a rate of 1 deg.C/min, oxidizing and crosslinking for 6h, cooling to obtain crosslinked asphalt with ether bond as main component, and FIG. 1 is solid nuclear magnetism of crosslinked asphalt 13 C NMR photographs;
(4) Transferring the crosslinked asphalt mainly containing ether bonds into a tubular furnace, and controlling the gas flow rate to be 120mL/min under the argon atmosphere; heating from room temperature to 1100 ℃, wherein the heating rate is 2 ℃/min, carbonizing for 2h, cooling to room temperature, washing with 1mol/L hydrochloric acid, absolute ethyl alcohol and water in sequence, filtering, and demagnetizing at 60 ℃, thus finally obtaining the asphalt-based hard carbon material with short-range ordered and long-range disordered microcrystalline structure, wherein FIG. 2 is a TEM photograph of the asphalt-based hard carbon.
The asphalt-based hard carbon material prepared in example 1 had La (carbon layer size) of 2.783nm, lc (carbon layer stack thickness) of 0.941nm, and d 002 (carbon layer spacing) was 0.382nm, and the structural parameters are shown in Table 1 below. Mixing the prepared asphalt-based hard carbon material with carbon black and polyvinylidene fluoride according to the mass ratio of 80. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1M NaClO 4 (the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1) solution is used as electrolyte to assemble the CR2032 button cell. Through tests, the current density of the hard carbon cathode is 20mA/g, the reversible specific capacity is 247.92mAh/g, the first coulombic efficiency is 78.61%, and the results are shown in the following table 2.
Example 2
(1) Crushing, grinding and sieving raw material asphalt to obtain an asphalt raw material with the particle size of 20 mu m;
(2) The ground and screened asphalt raw material is subjected to softening point determination and four-component analysis, and then screened to be used as a precursor with the softening point of 270 ℃;
(3) Placing the screened pitch precursor in a muffle furnace, and under the oxygen atmosphere, controlling the oxygen flow rate to be 100mL/min; heating to 325 deg.C from room temperature, heating at a rate of 1 deg.C/min, oxidizing and crosslinking for 12h, cooling to obtain crosslinked asphalt with ester group and acid anhydride as main components, and FIG. 3 shows crosslinked asphalt solidNuclear magnetism 13 C NMR photographs;
(4) Transferring the cross-linked asphalt mainly containing ester groups and acid anhydride into a tubular furnace, wherein the gas flow rate is 120mL/min under the argon atmosphere; heating from room temperature to 1100 ℃, wherein the heating rate is 2 ℃/min, carbonizing for 2h, cooling to room temperature, washing with 0.5mol/L hydrochloric acid, absolute ethyl alcohol and water in sequence, filtering, and demagnetizing at 60 ℃, so as to obtain the asphalt-based hard carbon material with a completely disordered stacked microcrystalline structure, wherein FIG. 4 is a TEM photograph of the asphalt-based hard carbon.
The asphalt-based hard carbon material prepared in example 2, the asphalt-based hard carbon crosslinked for 12h had La (carbon layer size) of 3.172nm, lc (carbon layer stack thickness) of 0.917nm, and d 002 (carbon layer spacing) was 0.392nm, and the structural parameters are shown in Table 1 below. Mixing the prepared asphalt-based hard carbon material with carbon black and polyvinylidene fluoride according to the mass ratio of 80. The cell was assembled in a glove box under Ar atmosphere, with metallic sodium as the counter electrode and 1M NaClO 4 (the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1) solution is used as electrolyte to assemble the CR2032 button cell. Through tests, the current density of the hard carbon cathode is 20mA/g, the reversible specific capacity of the asphalt-based hard carbon cathode crosslinked for 12 hours is 320.8mAh/g, the initial coulombic efficiency is 82.82%, and the results are shown in the following table 2. FIG. 5 is a first charge-discharge curve of pitch-based hard carbon negative electrode, wherein 325-6 represents a hard carbon negative electrode curve obtained by crosslinking at 325 ℃ for 6 hours, 325-9 represents a hard carbon negative electrode curve obtained by crosslinking at 325 ℃ for 9 hours, 325-12 represents a hard carbon negative electrode curve obtained by crosslinking at 325 ℃ for 12 hours, and 325-24 represents a hard carbon negative electrode curve obtained by crosslinking at 325 ℃ for 24 hours.
Example 3
(1) Crushing, grinding and sieving raw material asphalt to obtain an asphalt raw material with the particle size of 20 mu m;
(2) The ground and screened asphalt raw material is subjected to softening point determination and four-component analysis, and then screened to be used as a precursor with the softening point of 200 ℃;
(3) Placing the screened pitch precursor in a muffle furnace, and under the oxygen atmosphere, controlling the oxygen flow rate to be 50ml/min; heating to 200 ℃ from room temperature, wherein the heating rate is 5 ℃/min, oxidizing and crosslinking for 12h, and cooling to obtain crosslinked asphalt mainly containing ether bonds;
(4) Transferring the crosslinked asphalt mainly containing ether bonds into a tubular furnace, and controlling the gas flow rate to be 80mL/min under the argon atmosphere; heating the mixture from room temperature to 900 ℃, wherein the heating rate is 1 ℃/min, carbonizing for 10 hours, cooling to room temperature, washing with 0.5mol/L hydrochloric acid, absolute ethyl alcohol and water in sequence, filtering, and demagnetizing at 50 ℃ to finally obtain the pitch-based hard carbon material with short-range ordered and long-range disordered microcrystalline structures.
The asphalt-based hard carbon material prepared in example 3 had La (carbon layer size) of 2.91nm, lc (carbon layer stack thickness) of 0.971nm, and d 002 (carbon layer spacing) was 0.378nm, and the structural parameters are shown in Table 1 below. Mixing the prepared asphalt-based hard carbon material with carbon black and polyvinylidene fluoride according to the mass ratio of 80. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1M NaClO 4 And (the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1) solution is used as an electrolyte to assemble the CR2032 button cell. Through tests, the current density of the hard carbon cathode is 20mA/g, the reversible specific capacity is 228.8mAh/g, the initial coulombic efficiency is 82.74%, and the results are shown in Table 2 below.
Example 4
(1) Crushing, grinding and sieving raw material asphalt to obtain an asphalt raw material with the particle size of 15 mu m;
(2) The ground and screened asphalt raw material is subjected to softening point determination and four-component analysis, and then screened to be used as a precursor with the softening point of 300 ℃;
(3) Placing the screened pitch precursor in a muffle furnace, and under the oxygen atmosphere, controlling the oxygen flow rate to be 250mL/min; heating to 400 ℃ from room temperature, wherein the heating rate is 1 ℃/min, oxidizing and crosslinking for 6h, and cooling to obtain crosslinked asphalt mainly containing ester groups and acid anhydride;
(4) Transferring the cross-linked asphalt mainly containing ester groups and acid anhydride into a tubular furnace, wherein the gas flow rate is 120mL/min under the argon atmosphere; heating to 1600 ℃ from room temperature, heating at the rate of 10 ℃/min, carbonizing for 1h, cooling to room temperature, washing with 3mol/L acetic acid, absolute ethyl alcohol and water in sequence, filtering, and demagnetizing at 70 ℃ to finally obtain the pitch-based hard carbon material with the completely disordered stacked microcrystalline structure.
The asphalt-based hard carbon material prepared in example 4 had La (carbon layer size) of 3.46nm, lc (carbon layer stack thickness) of 0.874nm, and d 002 (carbon layer spacing) was 0.389nm, and the structural parameters are shown in Table 1 below. Mixing the prepared asphalt-based hard carbon material with carbon black and polyvinylidene fluoride according to the mass ratio of 80. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1M NaClO 4 (the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1) solution is used as electrolyte to assemble the CR2032 button cell. Tests prove that the current density of the hard carbon cathode is 20mA/g, the reversible specific capacity is 345.4mAh/g, the first coulombic efficiency is 80.93%, and the results are shown in the following table 2.
Example 5
(1) Crushing, grinding and sieving raw material asphalt to obtain an asphalt raw material with the particle size of 15 mu m;
(2) The ground and sieved asphalt raw material is subjected to softening point determination and four-component analysis, and then asphalt with the softening point of 270 ℃ is screened as a precursor;
(3) Placing the screened pitch precursor in a muffle furnace, and under the oxygen atmosphere, controlling the oxygen flow rate to be 90ml/min; heating to 270 ℃ from room temperature, wherein the heating rate is 2 ℃/min, oxidizing and crosslinking for 9 hours, and cooling to obtain crosslinked asphalt mainly containing ether bonds;
(4) Transferring the crosslinked asphalt mainly containing ether bonds into a tubular furnace, and controlling the gas flow rate to be 100mL/min under the argon atmosphere; heating from room temperature to 1200 ℃, wherein the heating rate is 3 ℃/min, carbonizing for 6h, cooling to room temperature, washing and filtering sequentially by 1mol/L hydrochloric acid, absolute ethyl alcohol and water, and demagnetizing at 60 ℃ to finally prepare the asphalt-based hard carbon material with short-range ordered and long-range disordered microcrystalline structures.
The La (carbon layer size) of the pitch-based hard carbon material prepared in example 5 was 2.834nm, lc (carbon layer stack thickness)Degree) of 0.930nm, d 002 (carbon layer spacing) was 0.383nm, and the structural parameters are shown in Table 1 below. Mixing the prepared asphalt-based hard carbon material with carbon black and polyvinylidene fluoride according to the mass ratio of 80. The cell was assembled in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1M NaClO 4 (the volume ratio of the ethylene carbonate to the diethyl carbonate is 1:1) solution is used as electrolyte to assemble the CR2032 button cell. Tests prove that the current density of the hard carbon cathode is 20mA/g, the reversible specific capacity is 265.9mAh/g, the first coulombic efficiency is 81.18%, and the results are shown in the following table 2.
Table 1 shows the carbon structure parameters of the negative electrode materials prepared in different examples;
| examples | Carbon layer spacing d002 (nm) | Crystallite size Lc (nm) | Crystallite size La (nm) |
| 1 | 0.382 | 0.941 | 2.783 |
| 2 | 0.392 | 0.917 | 3.172 |
| 3 | 0.378 | 0.971 | 2.91 |
| 4 | 0.389 | 0.874 | 3.46 |
| 5 | 0.383 | 0.930 | 2.834 |
Table 2 shows the relevant conditions and reversible specific capacities and first coulombic efficiencies of the negative electrode materials prepared in different examples;
those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (10)
1. The specific microcrystalline structure asphalt-based hard carbon is characterized in that La of the specific microcrystalline structure asphalt-based hard carbon is less than 3.5nm, and Lc of the specific microcrystalline structure asphalt-based hard carbon is less than 1nm; charring the cross-linked asphalt oxidized at 200-300 deg.C to obtain long-range disorder short-range ordered microcrystal structure of hard carbon 002 Between 0.37 and 0.385 nm; crosslinking by oxidation at 300-400 DEG CCharring the pitch to obtain a microcrystalline structure with hard carbon completely stacked in disorder, d 002 Between 0.38 and 0.395 nm.
2. The method for preparing the asphalt-based hard carbon with the specific microcrystalline structure according to claim 1, characterized by comprising the following steps of:
(1) Crushing, grinding and sieving raw material asphalt to obtain an asphalt raw material with the particle size of less than or equal to 20 mu m;
(2) The asphalt raw material in the step (1) is subjected to softening point determination and four-component analysis, and then an asphalt precursor is screened out;
(3) Placing the screened asphalt precursor in a muffle furnace, carrying out pre-oxidation crosslinking treatment in an oxygen-containing atmosphere for 6-12 h, and cooling to obtain differential crosslinked asphalt with oxygen-containing functional groups in different proportions;
(4) Transferring the differential cross-linked asphalt into a tubular furnace, carbonizing for 1-10 h under inert protective atmosphere, cooling to room temperature, washing, filtering and demagnetizing the carbonized hard carbon material to finally obtain the asphalt-based hard carbon material with the specific microcrystalline structure.
3. The method for preparing asphalt-based hard carbon with a specific microcrystalline structure according to claim 2, wherein the method for measuring the softening point in the step (2) is that the asphalt raw material is placed in a special test tube, is heated at a stable temperature rise rate under a nitrogen atmosphere, a steel needle bar with the diameter of 1mm is continuously used for pricking the asphalt in the process, and when the asphalt becomes soft and starts to adhere to the steel needle, the temperature at the moment is recorded, namely the softening point of the asphalt; dissolving and separating asphaltene by using n-heptane, adsorbing the asphaltene on an alumina color column, developing and washing by using n-heptane, toluene and toluene-ethanol in sequence to obtain saturated components, aromatic components and colloid in sequence; the pitch precursor needs to satisfy: the softening point is more than or equal to 200 ℃.
4. The method for preparing asphalt-based hard carbon with specific microcrystalline structure according to claim 2, wherein the oxygen-containing atmosphere in step (3) is one of air, pure oxygen or ozone, and the gas flow rate is 50-300 mL/min.
5. The method for preparing asphalt-based hard carbon with a specific microcrystalline structure according to claim 2, wherein the pre-oxidation crosslinking temperature in the step (3) is 200-400 ℃, and the heating rate is 1-5 ℃/min.
6. The method for preparing asphalt-based hard carbon with specific microcrystalline structure according to claim 5, wherein the functional groups with different oxygen contents in step (3) are one or more of acid anhydride, ester group, ether bond or ketone; wherein, the oxidative crosslinking at 200-300 ℃ mainly generates ether bonds; oxidizing and crosslinking at 300-400 deg.c to produce ester radical and acid anhydride as main component.
7. The method for preparing asphalt-based hard carbon with specific microcrystalline structure according to claim 2, wherein the inert protective atmosphere in step (4) is argon or nitrogen, and the gas flow rate is 80-120 mL/min.
8. The method for preparing asphalt-based hard carbon with a specific microcrystalline structure according to claim 2, wherein the carbonization temperature in the step (4) is 900-1600 ℃, and the temperature rise rate is 1-10 ℃/min.
9. The method for preparing the asphalt-based hard carbon with the specific microcrystalline structure according to claim 2, wherein the washing in the step (4) is sequentially washing with an acid solution, absolute ethyl alcohol and water; wherein the acid solution is selected from one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid, and the concentration of the acid solution is 0.5-3 mol/L; the temperature of the demagnetizing process is controlled to be 50-70 ℃.
10. The application of the asphalt-based hard carbon with the specific microcrystalline structure as claimed in claim 1, wherein the asphalt-based hard carbon with the specific microcrystalline structure can be used for the negative electrodes of sodium ion batteries, lithium ion batteries and potassium ion batteries.
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