CN112919434A - Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof - Google Patents
Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 title abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 5
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 claims abstract description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000005997 Calcium carbide Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- VHYBUUMUUNCHCK-UHFFFAOYSA-N 2,4,6-tribromo-1,3,5-triazine Chemical compound BrC1=NC(Br)=NC(Br)=N1 VHYBUUMUUNCHCK-UHFFFAOYSA-N 0.000 claims description 2
- RIRMMJBLWVZDJF-UHFFFAOYSA-N 2,4,6-triiodo-1,3,5-triazine Chemical compound IC1=NC(I)=NC(I)=N1 RIRMMJBLWVZDJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000006181 electrochemical material Substances 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract 1
- 230000002427 irreversible effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000011809 glassy carbon fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of electrochemical materials, and particularly relates to a secondary battery cathode material carbon-rich carbonitride and a preparation method and application thereof. The molecular structural formula of the carbon-rich carbonitride is C6N3Wherein, two ends of the ethynyl are respectively connected with the 2,4, 6-sites of the adjacent 1,3, 5-triazine, and an ordered close-packed regular hexagonal honeycomb structure consisting of 30 atoms is formed. The carbon-rich carbonitride is formed by sp and sp2Hybrid carbon and sp2Two-dimensional carbonitride composed of hybridized nitrogen and having pore volume of triazine ring g-C3N47.7 times of (a) or a heptazine ring g-C3N43.8 times of the total amount of the electrolyte, has a more open pore structure, can promote the interlayer migration of alkali metal ions, and is greatly beneficial to improving the performance of the secondary battery. So that the carbon-rich carbonThe nitride may be used as a negative electrode material for secondary batteries including lithium ion batteries, sodium ion batteries, and potassium ion batteries.
Description
Technical Field
The invention belongs to the technical field of electrochemical materials, and particularly relates to a carbon-rich carbonitride and a preparation method and application thereof.
Background
Graphite phase carbonNitride (C)xNy) Is a compound formed by carbon and nitrogen atoms (both sp)2Hybrid type) are ordered into two-dimensional materials (e.g., g-C)3N4、C3N5、C3N3、C4N4、C3N、C2N, etc.) which have a highly delocalized pi-conjugated system, unique periodic pore structure, good electrical, optical and physicochemical properties, have attracted extensive attention of researchers in the fields of photocatalysis, electrocatalysis, electrochemical energy storage, etc. CxNyCan be used for developing next-generation rechargeable secondary batteries with high power and high energy density.
The invention provides a method for synthesizing a protein by sp and sp2Hybrid carbon and sp2Two-dimensional carbon nitride (C) of hybridized nitrogen composition6N3) The pore volume of the triazine ring is g-C3N47.7 times of (a) or a heptazine ring g-C3N43.8 times of the total amount of the electrolyte, and a more open pore structure, can promote the interlayer migration of alkali metal ions, and is beneficial to improving the performance of the secondary battery.
Disclosure of Invention
The invention aims to provide a secondary battery cathode material carbon-rich carbonitride with excellent electrochemical performance, and a preparation method and application thereof.
The secondary battery cathode material carbon-rich carbon nitride provided by the invention has a molecular structural formula of C6N3Wherein, two ends of the ethynyl are respectively connected with the 2,4, 6-sites of the adjacent 1,3, 5-triazine, and an ordered close-packed regular hexagonal honeycomb structure consisting of 30 atoms is formed.
The carbon-rich carbonitride C provided by the invention6N3The preparation method comprises the following specific steps:
(1) weighing a certain amount of 2,4, 6-trihalo-1, 3, 5-triazine and calcium carbide, dispersing in absolute ethyl alcohol, transferring to a stainless steel ball milling tank, vacuumizing, filling argon gas, and sealing;
(2) placing the ball milling tank in a planetary ball mill, and carrying out ball milling for 12-24 hours at the speed of 500-600 revolutions per minute;
(3) the ball-milled product is put under the protection of argonAnnealing at 400-600 ℃ for 3-5 hours; immersing and washing the annealing product in a nitric acid solution of 0.1-0.15 mol/L for three times; vacuum drying at 60-80 ℃ for 12-24 hours to obtain C6N3。
In the above preparation process, the 2,4, 6-trihalo-1, 3, 5-triazine includes one or more of 2,4, 6-trichloro-1, 3, 5-triazine, 2,4, 6-tribromo-1, 3, 5-triazine and 2,4, 6-triiodo-1, 3, 5-triazine.
In the preparation process, the molar ratio of the 2,4, 6-trihalo-1, 3, 5-triazine to the calcium carbide is 1: 1.5-1: 10.
In the preparation process, the ratio of the total mass of the 2,4, 6-trihalo-1, 3, 5-triazine and the calcium carbide to the mass of the stainless steel ball grinding beads is 1: 30-1: 120.
In the preparation process, the volume of the absolute ethyl alcohol is 5-15% of the volume of the ball milling tank.
The present invention provides C prepared by the above process6N3。
In the present invention, C6N3Can be applied to negative electrode materials of lithium ion batteries, sodium ion batteries and potassium ion batteries.
The present invention proposes the use of sp and sp2Hybrid carbon and sp2Two-dimensional carbon nitride (C) of hybridized nitrogen composition6N3) The pore volume of the triazine ring is g-C3N47.7 times of (a) or a heptazine ring g-C3N43.8 times of the total amount of the electrolyte, and a more open pore structure, can promote the interlayer migration of alkali metal ions, and is greatly beneficial to improving the performance of the secondary battery. The material was measured at 100mA g-1The specific capacity of the lithium storage under the current density reaches 237mAh g-1At 50mA g-1The specific capacities of sodium storage and potassium storage under the current density are respectively 85mAh g-1And 128mAh g-1。
The carbon-rich carbonitride provided by the invention can be used as a negative electrode material of a secondary battery. The secondary battery includes a lithium ion battery, a sodium ion battery, and a potassium ion battery.
Drawings
FIG. 1 shows a schematic view of a process C according to the present invention6N3Schematic diagram of the molecular structure of (a).
Figure 2 is an XRD pattern of the product of example 1 of the invention.
FIG. 3 shows the charge and discharge curves of the first and second circles of the product of example 1 of the present invention as the negative electrode material of a lithium ion battery. The charge-discharge current density is 100mA g-1The voltage range is 0.01 to 3.0V (vs. Li/Li)+)。
Fig. 4 is the charge and discharge curves of the first and second circles of the product of example 2 of the present invention as the negative electrode material of sodium-ion battery. The charge-discharge current density is 50mA g-1The voltage range is 0.01-3.0V (vs. Na/Na)+)。
Fig. 5 shows the charge and discharge curves of the first and second circles of the product of example 3 of the present invention as the negative electrode material of potassium ion battery. The charge-discharge current density is 50mA g-1The voltage range is 0.01-3.0V (vs. K/K)+)。
Detailed Description
The present invention is further described below by way of examples of implementation, but is not limited thereto.
Example 1
Weighing 1.06 g of 2,4, 6-trichloro-1, 3, 5-triazine and 2.94 g of calcium carbide, dispersing in 15 ml of absolute ethyl alcohol, transferring to a stainless steel ball-milling tank (provided with 150 g of stainless steel balls) with the volume of 100 ml, vacuumizing, filling argon, and sealing; placing the ball milling tank in a planetary ball mill, setting the rotating speed to be 600 revolutions per minute, and carrying out ball milling for 12 hours; annealing the ball-milled product for 3 hours at 600 ℃ under the protection of argon; the annealed product was rinsed three times in 0.1 mol/l nitric acid solution; vacuum drying at 60 deg.C for 24 hours to obtain C6N3And (3) powder. The X-ray diffraction peak position shown in FIG. 2 matches the characteristic peak of graphite (Standard card No. 65-6212), indicating that C6N3Is a partially graphitized carbon material containing a small amount of silicon carbide (from the calcium carbide feedstock) impurities.
Weighing C in sequence according to the mass ratio of 8:1:16N3Dispersing powder, Super P conductive carbon and a polyvinylidene fluoride binder in a 1-methyl-2-pyrrolidone solvent, uniformly coating the slurry on a copper foil, drying in vacuum at 80 ℃ for 12 hours, and cutting into a wafer with the diameter of 14 mm as a working electrode. Assembled in a glove box filled with argonButton cell of CR2016 type, with lithium metal as counter electrode, 1 mol/l LiPF6Dispersed ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate (EC/DMC/EMC, volume ratio 1:1: 1) solution was used as electrolyte, Celgard-2300 diaphragm was used. Constant current charge and discharge test is carried out on the LAND test system, and the current density is 100mAg-1The voltage range is 0.01 to 3.0V (vs. Li/Li)+). FIG. 3 is the potential curves of the first and second circles during charging and discharging, the specific capacities of the first circle discharging and charging are 715 mAh g and 237mAh g respectively-1The irreversible capacity comes from an SEI film generated on the surface of the electrode and an irreversible lithium intercalation site; the reversible specific capacity of the second ring is 225 mAh g-1Corresponding to a coulombic efficiency of 82.4%.
Example 2
Weighing 1.48 g of 2,4, 6-trichloro-1, 3, 5-triazine and 4.10 g of calcium carbide, dispersing in 25 ml of absolute ethanol, transferring to a stainless steel ball-milling tank (provided with 375 g of stainless steel balls) with the volume of 250 ml, vacuumizing, filling argon, and sealing; placing the ball milling tank in a planetary ball mill, setting the rotating speed at 500 revolutions per minute, and carrying out ball milling for 20 hours; annealing the ball-milled product for 5 hours at 450 ℃ under the protection of argon; the annealed product was rinsed three times in 0.15 mol/l nitric acid solution; vacuum drying at 80 deg.C for 12 hr to obtain C6N3And (3) powder.
Weighing C in sequence according to the mass ratio of 8:1:16N3Dispersing powder, Super P conductive carbon and a polyvinylidene fluoride binder in a 1-methyl-2-pyrrolidone solvent, uniformly coating the slurry on a copper foil, drying in vacuum at 80 ℃ for 12 hours, and cutting into a wafer with the diameter of 14 mm as a working electrode. Assembled into a button cell of the CR2025 type in a glove box filled with argon, with sodium metal as the counter electrode, 1 mol/l NaClO4And 5% fluoroethylene carbonate (FEC) dispersed in ethylene carbonate/diethyl carbonate (EC/DEC, 1:1 by volume) solution as an electrolyte, using glassy carbon fiber GF/F as a separator. Constant current charge and discharge test is carried out on the LAND test system, and the current density is 50mAg-1The voltage range is 0.01-3.0V (vs. Na/Na)+). FIG. 4 is a graph showing potential curves of the first and second charge-discharge cycles, the first discharge cycle,The charging specific capacities are 533 and 85mAh g respectively-1The irreversible capacity comes from an SEI film generated on the surface of the electrode and an irreversible sodium storage site; the reversible specific capacity of the second ring is 78 mAh g-1Corresponding to a coulombic efficiency of 71.6%.
Example 3
Weighing 0.37 g of 2,4, 6-trichloro-1, 3, 5-triazine and 1.03 g of calcium carbide, dispersing in 15 ml of absolute ethyl alcohol, transferring to a stainless steel ball-milling tank (provided with 150 g of stainless steel balls) with the volume of 100 ml, vacuumizing, filling argon, and sealing; placing the ball milling tank in a planetary ball mill, setting the rotating speed to be 550 revolutions per minute, and carrying out ball milling for 16 hours; annealing the ball-milled product for 4 hours at 500 ℃ under the protection of argon; the annealed product was rinsed three times in 0.1 mol/l nitric acid solution; vacuum drying at 80 deg.C for 12 hr to obtain C6N3And (3) powder.
Weighing C in sequence according to the mass ratio of 8:1:16N3Dispersing powder, Super P conductive carbon and a polyvinylidene fluoride binder in a 1-methyl-2-pyrrolidone solvent, uniformly coating the slurry on a copper foil, drying in vacuum at 80 ℃ for 12 hours, and cutting into a wafer with the diameter of 14 mm as a working electrode. Button cell type CR2025 cell assembled in a glove box filled with argon, with potassium metal as the counter electrode, 0.8M KPF6Dispersed in ethylene carbonate/propylene carbonate (EC/PC, volume ratio of 1: 1) solution as electrolyte, and glassy carbon fiber GF/F as diaphragm. Constant current charge and discharge test is carried out on the LAND test system, and the current density is 50mAg-1The voltage range is 0.01-3.0V (vs. K/K)+). FIG. 5 is the potential curves of the first and second circles during charging and discharging, the first circle discharging and charging specific capacities are 444 mAh g and 128mAh g respectively-1The irreversible capacity comes from an SEI film generated on the surface of the electrode and an irreversible potassium storage site; the reversible specific capacity of the second ring is 111 mAh g-1Corresponding to a coulombic efficiency of 72.5%.
Claims (8)
1. The carbon-rich carbonitride is characterized in that the molecular structural formula is C6N3Wherein, the two ends of the ethynyl are respectively connected with the 2,4, 6-sites of the adjacent 1,3, 5-triazine, andan ordered close-packed regular hexagonal honeycomb structure consisting of 30 atoms was formed.
2. The method for preparing carbon-rich carbonitride of claim 1 comprising the specific steps of:
(1) weighing a certain amount of 2,4, 6-trihalo-1, 3, 5-triazine and calcium carbide, dispersing in absolute ethyl alcohol, transferring to a stainless steel ball milling tank, vacuumizing, filling argon gas, and sealing;
(2) placing the ball milling tank in a planetary ball mill, and carrying out ball milling for 12-24 hours at the speed of 500-600 revolutions per minute;
(3) annealing the ball-milled product for 3-5 hours at the temperature of 400-600 ℃ under the protection of argon; immersing and washing the annealing product in a nitric acid solution of 0.1-0.15 mol/L for three times; vacuum drying at 60-80 ℃ for 12-24 hours to obtain C6N3。
3. The method of claim 2, wherein the 2,4, 6-trihalo-1, 3, 5-triazine is selected from one or more of 2,4, 6-trichloro-1, 3, 5-triazine, 2,4, 6-tribromo-1, 3, 5-triazine, and 2,4, 6-triiodo-1, 3, 5-triazine.
4. The method of preparing a carbon-rich carbonitride of claim 2 wherein the molar ratio of the 2,4, 6-trihalo-1, 3, 5-triazine to the calcium carbide is 1:1.5 to 1: 10.
5. The method for preparing carbon-rich carbonitride according to claim 2 characterized in that the ratio of the total mass of the 2,4, 6-trihalo-1, 3, 5-triazine and the calcium carbide to the mass of the stainless steel beads is 1:30 to 1: 120.
6. The method of preparing a carbon-rich carbonitride of claim 2 wherein the volume of the absolute ethyl alcohol is 5 to 15 percent of the volume of the ball milling pot.
7. Use of the carbon-rich carbonitride of claim 1 in the preparation of a secondary battery anode material.
8. The use according to claim 7, wherein the secondary battery is a lithium ion battery, a sodium ion battery or a potassium ion battery.
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