CN116161644A - Preparation method and application of iodine doped sodium ion hard carbon - Google Patents
Preparation method and application of iodine doped sodium ion hard carbon Download PDFInfo
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- CN116161644A CN116161644A CN202310224231.XA CN202310224231A CN116161644A CN 116161644 A CN116161644 A CN 116161644A CN 202310224231 A CN202310224231 A CN 202310224231A CN 116161644 A CN116161644 A CN 116161644A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052740 iodine Inorganic materials 0.000 title claims description 20
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims description 19
- 239000011630 iodine Substances 0.000 title claims description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims description 8
- 229910001415 sodium ion Inorganic materials 0.000 title claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 79
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000002019 doping agent Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000197 pyrolysis Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 7
- 229940107816 ammonium iodide Drugs 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims description 5
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 claims description 5
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000007772 electrode material Substances 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 21
- 238000007605 air drying Methods 0.000 description 8
- 238000013507 mapping Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 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 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- DXZHSXGZOSIEBM-UHFFFAOYSA-M iodolead Chemical compound [Pb]I DXZHSXGZOSIEBM-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Images
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- 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
-
- 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
- H01M10/054—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of new energy storage materials, and particularly relates to a preparation method and application of an iodine-doped hard carbon material. The preparation method comprises the following steps of 1) preparing a precursor, namely carrying out hydrothermal treatment on a material, and then centrifuging and drying to obtain the precursor; 2) Dispersing into solution containing dopant, heating and stirring until the solvent is completely evaporated; 3) And carrying out high-temperature pyrolysis on the obtained product in an inert atmosphere at a certain heating rate to obtain the hard carbon material. The prepared material has rich active sites, can provide excellent performance as an electrode material, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of new energy storage materials, and particularly relates to a preparation method and application of an iodine-doped hard carbon material.
Background
Currently, sodium Ion Batteries (SIBs) have attracted widespread attention for large-scale energy storage due to the abundance of sodium resources worldwide. However, the development of low-cost and high-performance electrode materials is a key point for commercialization of sodium-based batteries. Fortunately, a series of high performance cathode materials for SIBs have been found, including layered oxides (P2 and O3 type layered oxides), tunnel oxides, phosphates and sulfates. In addition, the anode materials of SIBs have also been widely studied, including alloys, oxides, organic compounds, and carbon materials. So far, hard Carbon (HC) is one of the most promising anode materials for SIBs due to its low average potential and high reversible capacity. Therefore, HC prepared from glucose, PAN fiber, phenolic resin, resorcinol formaldehyde resin, and other polymers has attracted considerable research interest.
Disclosure of Invention
The invention aims to provide a preparation method and application of an iodine-doped hard carbon material. The method of the material adopted in the method is simple and low in cost, can provide excellent performance as an electrode material, and has wide application prospect.
In order to achieve the above object, the present invention has the following specific technical scheme:
the preparation method of the iodine doped hard carbon material comprises the following steps:
1) Dissolving raw materials in deionized water, transferring the raw materials into a polytetrafluoroethylene reaction kettle liner, then placing the raw materials into a stainless steel high-pressure kettle, reacting the raw materials at a high temperature for a period of time under a sealing condition, centrifugally cleaning the raw materials with the deionized water, and drying the raw materials by blowing until the moisture is completely volatilized;
2) Dispersing the product obtained in the step (1) into a solution containing a doping agent, heating and stirring until the solvent is completely evaporated;
3) And (3) carrying out high-temperature pyrolysis on the product obtained in the step (2) in an inert atmosphere at a certain heating rate to obtain the hard carbon material.
Further, the raw material in the step 1) is glucose or trehalose; the concentration after dissolution in deionized water is preferably 1 to 5M.
Further, the specification of the polytetrafluoroethylene reaction kettle liner in the step 1) is 10-1000mL, the high-temperature reaction temperature is 100-250 ℃, and the reaction time is 0.5-48 hours.
Further, the rotational speed of centrifugation in the centrifugal cleaning in the step 1) is 3000-12000 rmp, and the centrifugation time is 5-30 minutes.
Further, the temperature of the forced air drying in the step 1) is 60 to 120 ℃.
Further, the dopant in the step 2) is ammonium iodide or iodine, and the solvent used in the solution containing the dopant is deionized water; preferably, the concentration of the dopant-containing solution is 0.5-3.5M.
Further, the temperature of the heating and stirring in the step 2) is 80-130 ℃.
Further, the high-temperature pyrolysis temperature in the step 3) is 500-1600 ℃, the pyrolysis time is 0.5-12 h, and the heating rate is 0.5-10 ℃/min.
Another object of the present invention is to provide an iodine doped hard carbon material obtained by any one or any combination of the above technical solutions.
The invention also provides application of the iodine-doped hard carbon material in energy storage, such as preparation of a hard carbon anode of a sodium ion battery. The initial effect at 100mA/g of activation was 77.6% specific capacity 300mAh/g. At a current density of 1A/g, the specific capacity is 198mAh/g, which indicates that the material has excellent electrochemical performance.
Compared with the prior art, the invention has the beneficial effects that:
in the method, a simple hydrothermal method is utilized to prepare a hard carbon precursor, and the hard carbon precursor is put into a solution with a doping agent and dried. The method can lead iodine to be evenly dispersed in the material after doping, and the doping of hetero atoms increases the conductivity and the active site of the material.
The iodine doped hard carbon material prepared by the method has rich heteroatoms, can provide active sites to accelerate the reaction kinetics of the material, and has good physical and chemical properties and excellent conductivity, so that the iodine doped hard carbon material can be well applied to important fields such as lithium ion batteries, sodium ion batteries, lithium/sodium sulfur batteries, lithium/sodium selenium batteries, water-based batteries, air batteries, sensors, environmental purification, energy sources, catalysis and the like.
Drawings
FIG. 1 is an SEM image and a Mapping image of a hard carbon material obtained in example 1;
FIG. 2 is an SEM image and a Mapping image of the hard carbon material obtained in comparative example 1;
FIG. 3 is an SEM image and a Mapping image of the hard carbon material obtained in comparative example 2;
FIG. 4 is a TEM image of the hard carbon material obtained in example 1;
FIG. 5 is an XRD pattern of the hard carbon materials obtained in examples 1,2, 3 and 4, respectively;
FIG. 6 is an XRD pattern of the hard carbon materials obtained in comparative examples 1,2, and 3, respectively;
FIG. 7 is a graph showing the desorption of nitrogen from the resulting hard carbon materials obtained in examples 1,2, 3 and 4, respectively;
FIG. 8 is a first-turn charge-discharge curve of the hard carbon materials obtained in example 1 and comparative example 1;
FIG. 9 shows that the hard carbon obtained in example 1 and comparative examples 1,2 and 3 was 1A g -1 A cycle curve at current density of (C),
FIG. 10 is a charge-discharge curve of the hard carbon obtained in example 1 at a current density of 1A/g for different turns.
Detailed Description
The preparation method of the iodine doped hard carbon material comprises the following steps:
1) Dissolving raw materials in deionized water, transferring the raw materials into a polytetrafluoroethylene reaction kettle liner, then placing the raw materials into a stainless steel high-pressure kettle, reacting the raw materials at a high temperature for a period of time under a sealing condition, centrifugally cleaning the raw materials with the deionized water, and drying the raw materials by blowing until the moisture is completely volatilized;
2) Dispersing the product obtained in the step (1) into a solution containing a doping agent, heating and stirring until the solvent is completely evaporated;
3) And (3) carrying out high-temperature pyrolysis on the product obtained in the step (2) in an inert atmosphere at a certain heating rate to obtain the hard carbon material.
Further, the raw material in the step 1) is glucose or trehalose; the concentration after dissolution in deionized water is preferably 1 to 5M.
Further, the specification of the polytetrafluoroethylene reaction kettle liner in the step 1) is 10-1000mL, specifically 10mL, 50mL, 100mL, 200mL, 300mL, 400mL, 500mL, 600mL, 700mL, 800mL, 900mL, 1000mL and the like.
The high temperature reaction in step 1) is carried out at a temperature of 100 to 250℃and specifically 100℃and 110℃and 120℃and 130℃and 140℃and 150℃and 160℃and 170℃and 180℃and 190℃and 200℃and 210℃and 220℃and 230℃and 240℃and 250℃respectively; the reaction time is 0.5 to 48 hours, specifically 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours, 37 hours, 38 hours, 39 hours, 40 hours, 41 hours, 42 hours, 43 hours, 44 hours, 45 hours, 46 hours, 47 hours, 48 hours, and the like.
Further, the rotational speed of centrifugation in the step 1) is 3000-12000 rmp, specifically 3000rmp, 4000rmp, 5000rmp, 6000rmp, 7000rmp, 8000rmp, 9000rmp, 10000rmp, 11000rmp, 12000rmp, etc. during the centrifugal cleaning; the centrifugation time is 5 to 30 minutes, and specifically, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, and the like.
The temperature of the air drying in the step 1) is 60 to 120 ℃, specifically 60 ℃,70 ℃, 80 ℃,90 ℃, 100 ℃,110 ℃, 120 ℃ and the like.
Further, the dopant in the step 2) is ammonium iodide or iodine, and the solvent used in the solution containing the dopant is deionized water; preferably, the concentration of the dopant-containing solution is 0.5-3.5M.
The temperature of the heating and stirring in the step 2) is 80 to 130 ℃, specifically 80 ℃,90 ℃, 100 ℃,110 ℃, 120 ℃,130 ℃ and the like.
Further, the high-temperature pyrolysis in the step 3) has a temperature of 500 to 1600 ℃, specifically 500 ℃, 600 ℃,700 ℃, 800 ℃,900 ℃, 1000 ℃,1100 ℃, 1200 ℃,1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃ and the like; the pyrolysis time is 0.5-12 h, and can be specifically 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h and the like; the temperature rising rate is 0.5-10 ℃/min; specifically, it may be 0.5 deg.C/min, 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min, 10 deg.C/min, etc.
In order that the invention may be more readily understood, a further description of the process according to the invention will be provided below with reference to the accompanying drawings and the detailed description. It should not be construed that the scope of the above subject matter of the present invention is limited to the following examples.
In the following examples, the inert atmospheres described are all argon atmospheres. The agents used in this application are all commercially available products.
Example 1:
the preparation method of the iodine doped hard carbon material comprises the following steps:
(1) Dispersing 5g of glucose into 75mL of deionized water solution, transferring into a 100mL polytetrafluoroethylene reaction kettle liner, then placing into a stainless steel autoclave, reacting for 24 hours under a sealing condition and at a temperature of 150 ℃, centrifugally cleaning for 4 times by using deionized water, and drying overnight in a forced air drying oven at 80 ℃;
(2) Dispersing the product obtained in the step (1) in 100mL of 2.5M ammonium iodide solution, and heating and stirring the solution at the temperature of 125 ℃ until the water in the solution is completely volatilized;
(3) And (3) pyrolyzing the product obtained in the step (2) for 3 hours under the condition of inert atmosphere and 1500 ℃ with the heating rate of 3 ℃ per minute to obtain the hard carbon material No. 1.
The same method steps as in example 1 were used to prepare hard carbon materials, respectively, except that the sintering temperature was replaced with 500 ℃,700 ℃,900 ℃,1100 ℃,1300 ℃ or 1600 ℃, respectively; the properties exhibited by the resulting hard carbon material are shown in table 1.
Table 1:
the same procedure as in example 1 was used to prepare the hard carbon material, except that the concentration of ammonium iodide was adjusted to 0.5M,1.5M or 3.5M, respectively; the properties exhibited by the separately obtained hard carbon materials are shown in table 2.
TABLE 2
The same procedure as in example 1 was used to prepare the hard carbon material, respectively, except that the temperature of the hydrothermal treatment was replaced with 90 ℃,110 ℃,130 ℃ or 170 ℃. The properties exhibited by the resulting hard carbon material are shown in table 3.
TABLE 3 Table 3
Example 2:
the preparation method of the iodine doped hard carbon material comprises the following steps:
(1) Dispersing 5g of glucose into 75mL of deionized water solution, transferring into a 100mL polytetrafluoroethylene reaction kettle liner, then placing into a stainless steel autoclave, reacting for 24 hours under the conditions of sealing and 150 ℃, centrifugally cleaning for 4 times by using deionized water, and drying overnight at 80 ℃ in a forced air drying box;
(2) Dispersing the product obtained in the step (1) in 100mL of 2.5M iodine solution, heating and stirring until the water in the solution is completely volatilized;
(3) Pyrolyzing the product obtained in the step (2) for 3 hours under the condition of inert atmosphere and 1500 ℃ with the temperature rising rate of 3 ℃ per minute to obtain the hard carbon material No. 2.
The preparation of the hard carbon material was performed by the same procedure as in example 2, except that the concentration of iodine was adjusted to 0.5M,1.5M or 3.5M, respectively. The properties exhibited by the resulting hard carbon material are shown in table 4.
TABLE 4 Table 4
Example 3:
the preparation method of the iodine doped hard carbon material comprises the following steps:
(1) Dispersing 5g of trehalose into 75mL of deionized water solution, transferring into a 100mL polytetrafluoroethylene reaction kettle liner, then placing into a stainless steel autoclave, reacting for 24 hours under the conditions of sealing and 150 ℃, centrifugally cleaning for 4 times by using deionized water, and drying overnight at 80 ℃ in a forced air drying box;
(2) Dispersing the product obtained in the step (1) in 100mL of 2.5M ammonium iodide solution, heating and stirring until the water in the solution is completely volatilized;
(3) And (3) pyrolyzing the product obtained in the step (2) for 3 hours under the condition of inert atmosphere and 1500 ℃ with the temperature rising rate of 3 ℃ per minute to obtain the hard carbon material 3#.
The same procedure as in example 3 was used to prepare hard carbon materials, respectively, except that the sintering temperature was replaced with 500 ℃,700 ℃,900 ℃,1100 ℃,1300 ℃ or 1600 ℃. The properties exhibited by the resulting hard carbon material are shown in table 5.
Table 5:
the preparation of the hard carbon material was performed by the same procedure as in example 3, except that the concentration of ammonium iodide was adjusted to 0.5M,1.5M or 3.5M, respectively. The properties exhibited by the resulting hard carbon material are shown in table 6.
TABLE 6
The same procedure as in example 3 was used to prepare the hard carbon material, respectively, except that the temperature of the hydrothermal treatment was replaced with 90 ℃,110 ℃,130 ℃ or 170 ℃. The properties exhibited by the resulting hard carbon material are shown in table 7.
TABLE 7
Example 4:
the preparation method of the iodine doped hard carbon material comprises the following steps:
(1) Dispersing 5g of trehalose into 75mL of deionized water solution, transferring into a 100mL polytetrafluoroethylene reaction kettle liner, then placing into a stainless steel autoclave, reacting for 24 hours at 150 ℃ under a sealed condition, centrifugally cleaning for 4 times by using deionized water, and then drying overnight at 80 ℃ in a forced air drying oven;
(2) Dispersing the obtained product in 100mL of 2.5M iodine solution, heating and stirring until the water in the solution is completely volatilized;
(3) Pyrolyzing the product in an inert atmosphere at 1500 ℃ for 3 hours, wherein the heating rate is 3 ℃ per minute, so as to obtain a hard carbon material;
the preparation of the hard carbon material was performed by the same procedure as in example 4, except that the concentration of iodine was adjusted to 0.5M,1.5M or 3.5M, respectively. The properties exhibited by the resulting hard carbon material are shown in table 8.
TABLE 8
Comparative example 1:
the method for preparing the hard carbon material by the one-step method comprises the following steps:
5g of glucose is pyrolyzed for 3 hours at 1500 ℃ in an inert atmosphere, and the heating rate is 3 ℃ per minute, so that the hard carbon material is obtained.
Comparative example 2:
the preparation method of the hard carbon material comprises the following steps:
(1) Dispersing 5g of glucose into 75mL of deionized water solution, transferring into a 100mL polytetrafluoroethylene reaction kettle liner, then placing into a stainless steel autoclave, reacting for 24 hours at 150 ℃ under a sealed condition, centrifugally cleaning for 4 times by using deionized water, and then drying overnight at 80 ℃ in a forced air drying oven;
(2) And pyrolyzing the product in an inert atmosphere at 1500 ℃ for 3 hours, wherein the heating rate is 3 ℃ per minute, so as to obtain the hard carbon material.
The preparation of the hard carbon material was separately carried out using the same method steps as comparative example 2, except that the sintering temperature was adjusted to 500 ℃,700 ℃,900 ℃,1100 ℃,1300 ℃ or 1600 ℃. The properties exhibited by the resulting hard carbon material are shown in table 9.
TABLE 9
Comparative example 3:
a preparation method of a nitrogen-doped hard carbon material comprises the following steps:
(1) Dispersing 5g of glucose into 75mL of deionized water solution, transferring into a 100mL polytetrafluoroethylene reaction kettle liner, then placing into a stainless steel autoclave, reacting for 24 hours at 150 ℃ under a sealed condition, centrifugally cleaning for 4 times by using deionized water, and then drying overnight at 80 ℃ in a forced air drying oven;
(2) Dispersing the obtained product in 100mL of 2.5M urea solution, heating and stirring until the water in the solution is completely volatilized;
(3) Pyrolyzing the product in an inert atmosphere at 1500 ℃ for 3 hours, wherein the heating rate is 3 ℃ per minute, so as to obtain a hard carbon material;
experiment:
the hard carbon materials (1 #, 2#, 3#, 4 #) prepared in examples 1,2, 3, 4 respectively and the materials prepared in comparative examples 1,2, 3 respectively were prepared as negative electrodes of sodium ion batteries, respectively, and subjected to the related performance test.
The materials prepared in examples 1,2, 3 and 4 and comparative examples 1,2 and 3 were mixed with PVDF binder at a mass ratio of 90:10, and then added with an appropriate amount of NMP, ground to paste in an agate mortar, and coated on an aluminum current collector. The electrode active material was coated with a mass of about 2.5 mg. The electrode was then dried in vacuo at 120 ℃ for 12 hours to obtain a negative electrode for a sodium ion battery. And takes metal sodium as an anode and takes NaPF as electrolyte 6 in EC+DMC (vol%: 1:1), the voltage range is 0.01-3V. The charge and discharge tester was bond CT2001A. The specific results are shown in Table 5.
Table 10 comparative tables of electrochemical performances of examples 1,2, 3, 4, 5 and comparative examples 1, 2:
FIG. 1 is an SEM image of a hard carbon material (1#) obtained in example 1. The material is seen to be flaky and rough in surface by a low-power scanning electron microscope image, and the material can be seen to contain three elements C, O and I in a Mapping image.
Fig. 2 is an SEM image and Mapping image of the hard carbon material obtained in comparative example 1. It can be seen that the material is mainly composed of two elements, C and O.
Fig. 3 is an SEM image and Mapping image of the hard carbon material obtained in comparative example 2. It can be seen that the material is mainly composed of two elements, C and O.
FIG. 4 is a TEM image of the hard carbon material (1#) obtained in example 1. As can be seen from the transmission electron microscope image, the sheet layer is very thin and contains abundant micropores and mesopores. At the same time, a disordered lattice spacing of the hard carbon can be observed.
FIG. 5 is an XRD pattern of the hard carbon materials (1#, 2#, 3#, 4#) obtained in examples 1,2, 3 and 4. The wide Bao Yanshe peak at around 20 degrees can be seen to give a hard carbon material.
Fig. 6 is an XRD pattern of the hard carbon material obtained in comparative examples 1,2, and 3. The wide Bao Yanshe peak at around 20 degrees can be seen to give a hard carbon material.
FIG. 7 is a graph showing the desorption of nitrogen from the hard carbon materials (1#, 2#, 3#, 4#) obtained in examples 1,2, 3 and 4. The specific surface areas are respectively 12.5m 2 /g，13.6m 2 /g，13.3m 2 /g and 10.6m 2 /g。
Fig. 8 is a first-turn charge-discharge curve of the hard carbon material (1 #) obtained in example 1 and the hard carbon material obtained in comparative example 1. From the graph, at the same current density, comparative example 1 has no obvious plateau, and example 1 starts to plateau around 0.1V and gives higher capacity.
FIG. 9 shows that the hard carbon material (1#) obtained in example 1 and the hard carbon obtained in comparative examples 1,2 and 3 are 1Ag -1 Is a cycle curve at current density. As can be seen, the first effect of comparative examples 1,2 and 3 was 65.2, 64.2 and 80.1% respectively, the capacities were 115, 187 and 237mAh/g, and the first effect of example 1 was 77.6% and the specific capacity was 300mAh/g during activation of 100 mA/g. At a current density of 1A/g, the capacities of comparative examples 1,2 and 3 were 83, 113 and 182mAh/g, respectively, and the capacity of example 1 was 198mAh/g, indicating that the material had good electrochemical properties.
FIG. 10 is a charge-discharge curve of the hard carbon material (1#) obtained in example 1 at a current density of 1A/g for different turns. From the figure, the material has better cycle stability.
Finally, it is noted that the above-mentioned preferred embodiments are only intended to illustrate rather than limit the invention, and that, although the invention has been described in detail by means of the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the iodine-doped hard carbon material is characterized by comprising the following steps of:
1) Dissolving raw materials in deionized water to form a solution, transferring the solution into a polytetrafluoroethylene reaction kettle liner, then placing the solution into a stainless steel high-pressure kettle, reacting for a period of time at high temperature under a sealing condition, centrifugally cleaning the solution by using deionized water, and drying the solution by blowing until the moisture is completely volatilized;
2) Dispersing the product obtained in the step (1) into a solution containing a doping agent, heating and stirring until the solvent is completely evaporated;
3) And (3) carrying out high-temperature pyrolysis on the product obtained in the step (2) in an inert atmosphere at a certain heating rate to obtain the hard carbon material.
2. The method for preparing the iodine-doped porous hard carbon material according to claim 1, wherein: the raw material in the step 1) is glucose or trehalose.
3. The method for preparing the iodine-doped porous hard carbon material according to claim 1, wherein: the raw materials are dissolved in deionized water to form a solution with a concentration of 1-5M.
4. The method for preparing the iodine-doped porous hard carbon material according to claim 1, wherein: in the step 1), the specification of the reaction kettle is 10-1000mL, the high-temperature reaction temperature is 100-250 ℃, and the reaction time is 0.5-48 h; the centrifugal rotating speed is 3000-12000 rmp, and the centrifugal time is 5-30 minutes; the temperature of the blast drying is 60-120 ℃.
5. The method for preparing the iodine-doped hard carbon material according to claim 1, wherein: the doping agent in the step 2) is ammonium iodide or iodine; the solvent used for the dopant-containing solution is deionized water, and the concentration of the dopant-containing solution is 0.5-3.5M.
6. The method for preparing the iodine-doped hard carbon material according to claim 1, wherein: the temperature of heating and stirring in the step 2) is 80-130 ℃.
7. The method for preparing the iodine-doped hard carbon material according to claim 1, wherein: the inert atmosphere is argon atmosphere.
8. The method for preparing the iodine-doped hard carbon material according to claim 1, wherein: the high-temperature pyrolysis temperature in the step 3) is 500-1600 ℃, the pyrolysis time is 0.5-12 h, and the heating rate is 0.5-10 ℃/min.
9. An iodine doped hard carbon material prepared according to the method of any one of claims 1-8.
10. The use of an iodine doped hard carbon material according to claim 9, wherein: the iodine doped hard carbon material is used as an anode material of a sodium ion battery.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602064A (en) * | 2016-12-27 | 2017-04-26 | 深圳市川马电子股份有限公司 | Preparation method and application of iodine-doped graphene |
| CN113644269A (en) * | 2021-08-09 | 2021-11-12 | 西南大学 | Preparation method of nitrogen-doped hard carbon material, product and application thereof |
| WO2022032748A1 (en) * | 2020-08-14 | 2022-02-17 | 五邑大学 | Boron-doped mxene material and preparation method therefor |
| CN114671425A (en) * | 2022-01-07 | 2022-06-28 | 齐鲁工业大学 | Iodine-doped biomass-derived porous carbon composite material and preparation method thereof |
| CN115275189A (en) * | 2022-07-27 | 2022-11-01 | 云帆(镇江)新能源材料有限公司 | Nitrogen-doped rice hull-based hard carbon negative electrode material and preparation method and application thereof |
| CN115259150A (en) * | 2022-08-29 | 2022-11-01 | 江苏智纬电子科技有限公司 | Production process of biomass-based hard carbon material based on high-temperature sintering modification |
-
2023
- 2023-03-09 CN CN202310224231.XA patent/CN116161644A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602064A (en) * | 2016-12-27 | 2017-04-26 | 深圳市川马电子股份有限公司 | Preparation method and application of iodine-doped graphene |
| WO2022032748A1 (en) * | 2020-08-14 | 2022-02-17 | 五邑大学 | Boron-doped mxene material and preparation method therefor |
| CN113644269A (en) * | 2021-08-09 | 2021-11-12 | 西南大学 | Preparation method of nitrogen-doped hard carbon material, product and application thereof |
| CN114671425A (en) * | 2022-01-07 | 2022-06-28 | 齐鲁工业大学 | Iodine-doped biomass-derived porous carbon composite material and preparation method thereof |
| CN115275189A (en) * | 2022-07-27 | 2022-11-01 | 云帆(镇江)新能源材料有限公司 | Nitrogen-doped rice hull-based hard carbon negative electrode material and preparation method and application thereof |
| CN115259150A (en) * | 2022-08-29 | 2022-11-01 | 江苏智纬电子科技有限公司 | Production process of biomass-based hard carbon material based on high-temperature sintering modification |
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