CN115385323A - Heteroatom-doped biomass-derived hard carbon negative electrode material and preparation method thereof - Google Patents
Heteroatom-doped biomass-derived hard carbon negative electrode material and preparation method thereof Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 72
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 71
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 64
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 44
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000197 pyrolysis Methods 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
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- 238000000034 method Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
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- 239000004202 carbamide Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 4
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- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 20
- 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 3
- 239000011229 interlayer Substances 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract 1
- 241000209094 Oryza Species 0.000 description 18
- 235000007164 Oryza sativa Nutrition 0.000 description 18
- 235000009566 rice Nutrition 0.000 description 18
- 238000007605 air drying Methods 0.000 description 16
- 239000010405 anode material Substances 0.000 description 16
- 229910001415 sodium ion Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000010903 husk Substances 0.000 description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 230000002441 reversible effect Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
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- 238000004146 energy storage Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- 238000002484 cyclic voltammetry Methods 0.000 description 2
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- 239000004005 microsphere Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
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- 244000075850 Avena orientalis Species 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- -1 heteroatom organic compound Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a heteroatom-doped biomass-derived hard carbon negative electrode material and a preparation method thereof, wherein biomass is cleaned and dried to obtain a biomass precursor, the biomass precursor is carbonized in the air atmosphere, and is ground after being cooled to obtain a pre-carbonized product; uniformly mixing the pre-carbonized product and an organic compound containing heteroatoms in proportion, and placing the obtained mixture into a hydrothermal reaction kettle for hydrothermal reaction to obtain a heteroatom-doped hard carbon material precursor; and transferring the heteroatom-doped biomass precursor into an atmosphere furnace, carrying out pyrolysis carbonization under the protection of inert gas, cooling, placing the cooled biomass precursor into an acid solution, washing the cooled biomass precursor to be neutral, and carrying out vacuum drying on the obtained product to obtain the heteroatom-doped hard carbon material. The invention effectively improves the interlayer spacing of the material, provides more active sites, and improves the sodium storage performance of the hard carbon material, thereby effectively improving the electrochemical performance of the biological hard carbon cathode material.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials of sodium-ion batteries, and particularly relates to a heteroatom-doped biomass-derived hard carbon negative electrode material for a sodium-ion battery and a preparation method thereof.
Background
With the development of the lithium ion electric automobile industry, the demand for lithium resources is increasing day by day, while the content of lithium in the earth crust is very limited (only 0.002%) and the distribution is uneven, and lithium not only faces to the price increase but also has the problem of resource shortage, and can not meet the energy storage demand. Therefore, the development of a battery energy storage system with low cost, high capacity and sustainable development is of great significance. Sodium and lithium belong to adjacent elements of a first main group, have similar physical and chemical properties, are rich in sodium ion resources, are low in price and have no pollution to the environment, so that the attention of extensive researchers and the industry is attracted. Researches show that the potential of sodium ions is about 0.3V higher than that of lithium ions, and the safety performance of the lithium ion battery is superior to that of a lithium ion battery. Therefore, in recent years, research on sodium ion batteries has progressed rapidly, and sodium ion batteries are more likely to become large-scale energy storage base stations.
The hard carbon material has large interlayer spacing and specific surface area, and shows advantages of high capacity, low potential and the like, so that the hard carbon material is widely concerned by researchers and is considered to be one of the most promising negative electrode materials of the sodium-ion battery. The biomass material is used as one of precursors of the hard carbon material, has a natural microstructure and is rich in carbon elements, and the derived carbon material has large interlamellar spacing, high disorder degree and rich active sites, has the advantages of low cost, reproducibility, environmental protection and the like, draws wide attention and is regarded as a reliable large-scale carbon source.
In the research report of hard carbon materials, heteroatom doping is considered to be an effective method for effectively improving the electrochemical performance of the hard carbon negative electrode material of the sodium ion battery. Yan and the like utilize oats as a carbon source and a nitrogen source, prepare the nitrogen-doped carbon microspheres by a simple hydrothermal method, have higher reversible specific capacity and good circulation stability, and still have the reversible specific capacity of 104mA h/g after being circulated for 12500 times under the current density of 10A/g. Hu and the like prepare nitrogen-doped carbon fiber materials by using an electrostatic spinning method, provide 293mAh/g high reversible capacity at a current density of 50mA/g, have 64 percent of coulombic efficiency and simultaneously show excellent multiplying power and cycle performance. Wang also prepared a porous nitrogen-doped microsphere material which still had excellent cycling stability of 206mAh/g after 600 cycles at a current density of 0.2A/g and high rate capability of 155mAh/g at a current density of 1A/g. Most methods for doping a hard carbon material with a heteroatom organic compound are focused on methods such as a hydrothermal method and a one-step pyrolysis method, most of the doped materials can obviously improve the electrochemical performance of the material, but the problems of insufficient capacity, low first coulombic efficiency and the like still exist, and therefore, the improvement of the capacity and the first coulombic efficiency of the material becomes one of the key problems of the hard carbon material.
Disclosure of Invention
The invention aims to solve the technical problem of providing a heteroatom-doped biomass-derived hard carbon negative electrode material and a preparation method thereof, so as to further improve the capacity and the first coulombic efficiency of the material.
In order to solve the above technical problems, according to an aspect of the present invention, there is provided a method for preparing a heteroatom-doped biomass-derived hard carbon anode material, comprising:
cleaning and drying biomass to obtain a biomass precursor, wherein the biomass raw material is one or a combination of more than two of straw, rice husk and rape;
carbonizing the biomass precursor in an air atmosphere, cooling, and grinding to obtain a pre-carbonized product;
step three: uniformly mixing the pre-carbonized product and an organic compound containing heteroatoms in proportion, placing the obtained mixture into a hydrothermal reaction kettle for hydrothermal reaction, wherein the hydrothermal heat preservation time is 18-24 hours, and the hydrothermal temperature is 120-180 ℃, so as to obtain a heteroatom-doped hard carbon material precursor;
step four: transferring the heteroatom-doped biomass precursor into an atmosphere furnace, carrying out pyrolysis carbonization under the protection of inert gas, wherein the heating rate is 1-5 ℃/min, the pyrolysis temperature is 800-1200 ℃, the heat preservation time is 2-4 hours, placing the biomass precursor into an acid solution after cooling, then washing the biomass precursor to be neutral, and carrying out vacuum drying on the obtained product to obtain the heteroatom-doped hard carbon material.
Further, in the first step, the biomass is placed in deionized water for washing, and the washed biomass is placed in a forced air drying oven for drying at the drying temperature of 80 ℃ for 12 hours to obtain the biomass precursor.
Further, in the second step, during carbonization, the temperature rise rate is 5-10 ℃/min, the pyrolysis temperature is 300-400 ℃, and the heat preservation time is 2-4 hours.
Further, in the third step, the organic compound containing hetero atoms is selected from one or more of urea, melamine, sodium dihydrogen phosphate, thiourea and dicyandiamide.
Further, the mass ratio of the organic compound containing a hetero atom to the pre-carbonized product is 0.1 to 1.
Further, in the fourth step, the temperature is raised to 1100 ℃ at a temperature raising rate of 5 ℃/min during pyrolysis and carbonization.
Further, in the fourth step, the inert gas is selected from one of nitrogen, argon or helium.
Further, in the fourth step, the concentration of the acid solution is 1-2mol/L, the soaking time is 6-12 hours, and the acid solution is selected from one of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid.
Further, in the fourth step, the vacuum drying temperature is 80 ℃, and the drying time is 12 hours.
According to another aspect of the present invention, there is provided a heteroatom-doped biomass-derived hard carbon anode material, characterized in that: obtained by the preparation method described above.
According to the invention, by using a method of low-temperature hydrothermal assisted heteroatom doping, the interlayer spacing of the material is effectively improved, more active sites are provided, and the sodium storage performance of the hard carbon material is improved, so that the electrochemical properties of the biological hard carbon negative electrode material, such as reversible capacity and first-turn coulombic efficiency, are effectively improved.
The preparation method is simple, low in cost, environment-friendly and suitable for large-scale production.
Drawings
FIG. 1 is a cyclic voltammogram of a heteroatom-doped biomass-derived hard carbon anode material prepared in example 2 of the present invention at a scan rate of 0.1 mv/s;
fig. 2 is a plot of cyclic voltammetry at different scan rates for the heteroatom-doped biomass-derived hard carbon anode material prepared in example 2 of the present invention;
fig. 3 is a first-turn charge-discharge curve diagram of the heteroatom-doped derivative biomass-derived hard carbon anode material prepared in example 2 of the present invention;
fig. 4 is a graph of cycle performance of the heteroatom-doped biomass-derived hard carbon anode material prepared in example 2 of the present invention;
fig. 5 is a graph of rate performance of a heteroatom-doped biomass-derived hard carbon anode material prepared in example 2 of the present invention;
fig. 6 is a TEM image of a biomass-derived hard carbon anode material prepared in example 2 of the present invention;
fig. 7 is an SEM image of a biomass-derived hard carbon anode material prepared in example 2 of the present invention;
fig. 8 is an XRD pattern of the biomass-derived hard carbon anode materials prepared in example 2 of the present invention and comparative example 1.
Detailed Description
The method of the present invention is explained and illustrated in detail below by examples, which are provided for a better understanding of the present disclosure, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all the technologies realized based on the above-described contents of the present invention belong to the scope of the present invention.
Example 1
(1) The selected biomass material is rice hull, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) Mixing the pre-carbonized product obtained in the step (2) with melamine according to a mass ratio of 4:1, placing the obtained mixture in a hydrothermal kettle, and preserving heat for 18 hours at the temperature of 180 ℃ to obtain a nitrogen-doped hard carbon material precursor;
(4) And (4) transferring the precursor of the nitrogen-doped hard carbon material obtained in the step (3) into an atmosphere furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving the heat for 3 hours, naturally cooling, placing the precursor into a 1M dilute hydrochloric acid solution, soaking for 6 hours, washing to be neutral, and placing the obtained product into a forced air drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the nitrogen-doped hard carbon material.
Example 2
(1) The selected biomass material is rice hull, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) Mixing the pre-carbonized product obtained in the step (2) with urea according to a mass ratio of 4:1, placing the obtained mixture in a hydrothermal kettle, and preserving heat for 18 hours at the temperature of 180 ℃ to obtain a nitrogen-doped hard carbon material precursor;
(4) And (4) transferring the precursor of the nitrogen-doped hard carbon material obtained in the step (3) into an atmosphere furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving the heat for 3 hours, naturally cooling, placing the precursor into a 1M dilute hydrochloric acid solution, soaking for 6 hours, washing to be neutral, and placing the obtained product into a forced air drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the nitrogen-doped hard carbon material.
Example 3
(1) The selected biomass material is rice hull, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) And (3) mixing the pre-carbonized product obtained in the step (2) with sodium dihydrogen phosphate according to a mass ratio of 4:1, placing the obtained mixture in a hydrothermal kettle, and preserving heat for 18 hours at the temperature of 180 ℃ to obtain a precursor of the phosphorus-doped hard carbon material;
(4) And (4) transferring the nitrogen-doped hard carbon material precursor obtained in the step (3) into an atmosphere furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat for 3 hours, naturally cooling, placing into a 1M dilute hydrochloric acid solution, soaking for 6 hours, washing to neutrality, placing the obtained product into a forced air drying oven, and drying in vacuum at 80 ℃ for 12 hours to obtain the phosphorus-doped hard carbon material.
Example 4
(1) The selected biomass material is rice hull, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) Mixing the pre-carbonized product obtained in the step (2) with boric acid according to the mass ratio of 4:1, placing the obtained mixture in a hydrothermal kettle, and preserving heat for 18 hours at the temperature of 180 ℃ to obtain a boron-doped hard carbon material precursor;
(4) And (4) transferring the nitrogen-doped hard carbon material precursor obtained in the step (3) into an atmosphere furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving the heat for 3 hours, naturally cooling, placing the precursor into a 1M dilute hydrochloric acid solution, soaking for 6 hours, washing to be neutral, and placing the obtained product into an air-blowing drying oven for vacuum drying for 12 hours at 80 ℃ to obtain the boron-doped hard carbon material.
Example 5
(1) The selected biomass material is rice hull, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) Mixing the pre-carbonized product obtained in the step (2) with sulfuric acid according to a mass ratio of 4:1, placing the obtained mixture in a hydrothermal kettle, and preserving heat for 18 hours at the temperature of 180 ℃ to obtain a sulfur-doped hard carbon material precursor;
(4) And (4) transferring the nitrogen-doped hard carbon material precursor obtained in the step (3) into an atmosphere furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving the heat for 3 hours, naturally cooling, placing the precursor into a 1M dilute hydrochloric acid solution, soaking for 6 hours, washing to be neutral, and placing the obtained product into an air-blowing drying oven for vacuum drying for 12 hours at 80 ℃ to obtain the sulfur-doped hard carbon material.
Example 6
(1) The selected biomass material is rice hull, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) Mixing the pre-carbonized product obtained in the step (2) with thiourea according to a mass ratio of 4:1, placing the obtained mixture in a hydrothermal kettle, and preserving heat for 18 hours at the temperature of 180 ℃ to obtain a nitrogen-doped hard carbon material precursor;
(4) And (4) transferring the nitrogen-doped hard carbon material precursor obtained in the step (3) into an atmosphere furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat for 3 hours, naturally cooling, placing the precursor into a 1M dilute hydrochloric acid solution, soaking for 6 hours, washing to be neutral, placing the obtained product into a forced air drying oven, and drying in vacuum at 80 ℃ for 12 hours to obtain the nitrogen-sulfur co-doped hard carbon material.
Example 7
(1) The selected biomass material is rice hull, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) Mixing the pre-carbonized product obtained in the step (2) with urea according to the mass ratio of 1:1, placing the obtained mixture in a hydrothermal kettle, and preserving heat for 18 hours at the temperature of 180 ℃ to obtain a nitrogen-doped hard carbon material precursor;
(4) And (4) transferring the precursor of the nitrogen-doped hard carbon material obtained in the step (3) into an atmosphere furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving the heat for 3 hours, naturally cooling, placing the precursor into a 1M dilute hydrochloric acid solution, soaking for 6 hours, washing to be neutral, and placing the obtained product into a forced air drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the nitrogen-doped hard carbon material.
Example 8
(1) The selected biomass material is rice hull, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 10 ℃/min in the atmosphere of air, preserving heat for 4 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) Mixing the pre-carbonized product obtained in the step (2) with urea according to the mass ratio of 10:1, placing the obtained mixture in a hydrothermal kettle, and preserving heat for 24 hours at the temperature of 120 ℃ to obtain a nitrogen-doped hard carbon material precursor;
(4) And (4) transferring the precursor of the nitrogen-doped hard carbon material obtained in the step (3) into an atmosphere furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving the heat for 3 hours, naturally cooling, placing the precursor into a dilute hydrochloric acid solution with the concentration of 2M, soaking for 12 hours, washing to be neutral, and placing the obtained product into a forced air drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the nitrogen-doped hard carbon material.
Comparative example 1
This comparative example provides a method of preparing an undoped hard carbon material.
(1) The selected biomass is rice husk, washed by deionized water for 6 hours, and then placed in a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor.
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, and grinding to powder to obtain a pre-carbonized product;
(3) Placing the pre-carbonized product obtained in the step (2) in a hydrothermal kettle, and preserving heat for 18 hours at the temperature of 180 ℃ to obtain a nitrogen-doped hard carbon material precursor;
(4) And (4) transferring the nitrogen-doped hard carbon material precursor obtained in the step (3) into a high-temperature tube furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat for 3 hours, naturally cooling, placing into a 1M dilute hydrochloric acid solution, soaking for 6 hours, washing to neutrality, and placing the obtained product into an air-blowing drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the hard carbon material.
The biomass-derived hard carbon materials obtained in examples and comparative examples were uniformly ground with acetylene black and polyvinylidene fluoride (PVDF) at a mass ratio of 8.
The electrode plate obtained above was used as a negative electrode, a glass fiber (Whitman, GF/D) disc with a diameter of 19mm was used as a separator, a sodium metal sheet with a diameter of 12mm and a thickness of 0.2mm was used as a counter electrode and a reference electrode, an electrolyte was a 1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution, a sodium ion battery was assembled in a glove box filled with high purity argon gas according to the structure of a CR2016 standard button cell, and the battery was subjected to a charge and discharge test with a current density of 25mA/g on a battery test platform.
TABLE 1 main parameters and electrochemical Properties of examples 1-6
| Biomass | Doping type/agent | Pyrolysis temperature/time | Initial specific capacity | First coulombic efficiency | |
| Example 1 | Rice husk | Nitrogen doped/melamine | 1100℃/3h | 278.2mAh/g | 61.95% |
| Example 2 | Rice husk | Nitrogen doped/urea | 1100℃/3h | 336.7mAh/g | 67.43% |
| Example 3 | Rice husk | Phosphorus doped/sodium dihydrogen phosphate | 1100℃/3h | 256.7mAh/g | 62.92% |
| Example 4 | Rice husk | Boron doped/boric acid | 1100℃/3h | 262.7mAh/g | 61.43% |
| Example 5 | Rice husk | Sulfur doped/sulfuric acid | 1100℃/3h | 271.5mAh/g | 63.24% |
| Example 6 | Rice husk | Nitrogen and sulfur co-doping/thiourea | 1100℃/2h | 287.9 mAh/g | 62.41% |
| Example 7 | Rice husk | Nitrogen doped/urea | 1100℃/3h | 289.1 mAh/g | 65.4% |
| Comparative example 1 | Rice husk | Is not doped | 1100℃/3h | 252.7mAh/g | 61.39% |
The CV graphs shown in fig. 1 and 2 show that the hard carbon anode material prepared in example 2 has good cyclability in a sodium ion battery, and the curves of the second circle and the third circle almost coincide after the first circle of cycling, which indicates that the material has high electrochemical reversibility.
As can be seen from the charge and discharge graph shown in fig. 3, the hard carbon negative electrode material prepared in example 2 shows 67.43% of first-turn coulombic efficiency and 336.7mAh/g of initial specific capacity in the voltage region of 0-3V at a current density of 20mA/g, and has a significant charge and discharge platform.
It can be seen from the long cycle performance graph shown in fig. 4 that the hard carbon anode material prepared in example 2 shows good cycle stability and capacity retention rate.
The rate performance graph shown in fig. 5 shows that the hard carbon anode material prepared in example 2 can show good rate performance at 25mA/g, 50mA/g, 75 mA/g, 100 mA/g, 200 mA/g and then return to 25 mA/g.
It can be seen from the TEM and SEM pictures shown in fig. 6 and 7 that example 2 shows a pore-like structure with micron, and surface defects can be improved by doping nitrogen element, which is beneficial to the storage of sodium ions, thereby increasing the reversible capacity of the material.
As can be seen from the XRD patterns shown in fig. 8, the hard carbon anode material prepared in example 2 and the hard carbon anode material prepared in comparative example 1 both exhibited diffraction peaks at diffraction angles of about 24 ° and 43.9 °, corresponding to the (002) and (101) crystal planes of a typical hard carbon structure. The (002) peak of the nitrogen-doped hard carbon anode material prepared in example 2 was broader than that of the material prepared in comparative example 1, indicating that nitrogen doping can form more defects.
Claims (10)
1. A preparation method of a heteroatom-doped biomass-derived hard carbon negative electrode material is characterized by comprising the following steps of:
cleaning and drying biomass to obtain a biomass precursor;
carbonizing the biomass precursor in an air atmosphere, cooling and grinding to obtain a pre-carbonized product;
step three: uniformly mixing the pre-carbonized product and an organic compound containing heteroatoms in proportion, placing the obtained mixture into a hydrothermal reaction kettle for hydrothermal reaction, wherein the hydrothermal heat preservation time is 18-24 hours, and the hydrothermal temperature is 120-180 ℃, so as to obtain a heteroatom-doped hard carbon material precursor;
step four: transferring the heteroatom-doped biomass precursor into an atmosphere furnace, carrying out pyrolysis carbonization under the protection of inert gas, wherein the heating rate is 1-5 ℃/min, the pyrolysis temperature is 800-1200 ℃, the heat preservation time is 2-4 hours, placing the biomass precursor into an acid solution after cooling, then washing the biomass precursor to be neutral, and carrying out vacuum drying on the obtained product to obtain the heteroatom-doped hard carbon material.
2. The method of claim 1, wherein: and step one, placing the biomass in deionized water for washing, placing the washed biomass in a blast drying oven for drying at the drying temperature of 80 ℃ for 12 hours to obtain a biomass precursor.
3. The production method according to claim 1 or 2, characterized in that: in the second step, during carbonization, the heating rate is 5-10 ℃/min, the pyrolysis temperature is 300-400 ℃, and the heat preservation time is 2-4 hours.
4. The production method according to claim 3, characterized in that: in the third step, the organic compound containing hetero atoms is selected from one or more of urea, melamine, sodium dihydrogen phosphate, thiourea and dicyandiamide.
5. The method of claim 4, wherein: the mass ratio of the organic compound containing hetero atoms to the pre-carbonized product is 0.1 to 1.
6. The production method according to claim 1 or 5, characterized in that: in the fourth step, the temperature is raised to 1100 ℃ at the temperature rise rate of 5 ℃/min during pyrolysis and carbonization.
7. The method of claim 6, wherein: in the fourth step, the inert gas is selected from one of nitrogen, argon or helium.
8. The method of claim 7, wherein: in the fourth step, the concentration of the acid solution is 1-2mol/L, and the soaking time is 6-12 hours.
9. The method of claim 8, wherein: in the fourth step, the vacuum drying temperature is 80 ℃, and the drying time is 12 hours.
10. A heteroatom-doped biomass-derived hard carbon negative electrode material is characterized in that: obtained by the production method according to any one of claims 1 to 9.
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