CN112786880A - Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof - Google Patents
Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of advanced materials, and particularly relates to a graphite monoalkyne derivative with a rhombic pore structure, and a preparation method and application thereof. The rhombic hole graphite single alkyne derivative has the molecular structure characteristics that: two ends of the ethynyl are respectively connected with 1,2,4, 5-sites (2, 3,5, 6-sites) of adjacent six-membered conjugated cyclic compounds to form an ordered close-packed approximate rhombic pore structure consisting of 18 atoms; the pore volume of the material is twice of that of gamma-type graphite single alkyne and naphthylalkyne, the material has excellent electrochemical performance, and can be used for preparing cathode materials of lithium ion batteries, sodium ion batteries and potassium ion batteries.
Description
Technical Field
The invention belongs to the technical field of advanced materials, and particularly relates to a graphite monoalkyne derivative with a rhombic pore structure, and a preparation method and application thereof.
Background
The gamma-type graphite single alkyne is composed of sp and sp2The novel carbon allotrope consisting of hybridized carbon atoms can be regarded as being formed by connecting ethynyl with adjacent benzene rings, and has a two-dimensional plane conjugated system, rich ethynyl functional groups,The structure of the single large triangular hole and good chemical stability have wide application prospect in the fields of energy conversion (such as photocatalytic hydrogen production and electrochemical water decomposition) and storage (such as secondary batteries and super capacitors). The carbon layer spacing (0.36-0.38 nm) of the gamma-type graphite monoacyne is larger than that of graphite (0.335 nm), so that lithium/sodium/potassium ion intercalation reaction and in-layer diffusion are facilitated; and ordered pore channels in the molecular structure can provide additional lithium/sodium/potassium storage active sites and promote the interlayer migration of metal ions. Therefore, the gamma-type graphite single alkyne is an alkali metal ion battery negative electrode material with development prospect.
The construction of the carbon skeleton-based large-aperture and high-pore volume ordered pore canal is important for realizing the rapid diffusion/migration of lithium/sodium/potassium ions in a three-dimensional space. Patents CN108083272A and CN108373147A propose the preparation of gamma-type graphite monoalkyne by using hexahalobenzene and calcium carbide as precursors. Patent CN108946698A proposes to prepare gamma-type graphite monoalkyne by using cheap benzene instead of the above-mentioned hexa-halogenobenzene organic precursor. Patent CN109626368A, CN111137875A report respectively that graphite monoalkyne is doped with hetero atoms, but the pore structures are randomly distributed or the pore sizes are different, so that three-dimensional ordered pore channels cannot be effectively constructed. Patent CN110371946A reports a gamma-type graphitic monoalkyne analogue (naphthylyne) with intrinsically ordered pore channels but no actual pore volume enhancement.
The invention provides a graphite monoalkyne derivative with a rhombic pore structure, wherein the pore volume of the graphite monoalkyne derivative is twice that of gamma-type graphite monoalkyne and naphthylalkyne.
Disclosure of Invention
The invention aims to provide a graphite monoalkyne derivative with a rhombic pore structure (hereinafter, the graphite monoalkyne derivative is marked as 'rhombic pore graphite monoalkyne derivative') and a preparation method thereof, and the material is used as a negative electrode material and applied to lithium ion batteries, sodium ion batteries and potassium ion batteries.
The invention provides a rhombic hole graphite single alkyne derivative, which has the molecular structure characteristics that: two ends of the ethynyl are respectively connected with 1,2,4, 5-sites (or 2,3,5, 6-sites) of adjacent six-membered conjugated cyclic compounds to form an ordered close-packed approximate rhombic pore structure consisting of 18 atoms.
The invention provides a preparation method of a rhombic hole graphite single alkyne derivative, which comprises the following specific steps:
(1) dispersing a certain amount of hexahydric conjugated cyclic compound with specific substitution sites and calcium carbide in absolute ethyl alcohol, transferring the solution to a stainless steel ball milling tank, vacuumizing, filling argon, and sealing;
(2) placing the ball milling tank in a planetary ball mill, and operating at the speed of 500-600 revolutions per minute for 12-24 hours;
(3) annealing the ball-milled product for 3-5 hours at the temperature of 400-600 ℃ under the protection of argon;
(4) immersing and washing the annealing product in a nitric acid solution of 0.1-0.15 mol/L for 2-4 times;
(5) and (3) drying the mixture in vacuum at the temperature of between 60 and 80 ℃ for 12 to 24 hours to obtain the rhombic porous graphite monoalkyne derivative.
In the present invention, the six-membered conjugated cyclic compound having a specific substitution site includes one or more of 1,2,4, 5-tetrachlorobenzene, 1,2,4, 5-tetrabromobenzene, 1,2,4, 5-tetraiodobenzene, 2,3,5, 6-tetrachloropyridine, 2,3,5, 6-tetrabromopyridine, 2,3,5, 6-tetraiodopyridine, pyrazine, 2,3,5, 6-tetrachloropyrazine, 2,3,5, 6-tetrabromopyrazine, 2,3,5, 6-tetraiodopyrazine.
In the present invention, the molar ratio of the six-membered conjugated cyclic compound to calcium carbide is 1:2 to 1:10 (1: 2 to 10)).
In the present invention, the ratio of the total mass of the six-membered conjugated cyclic compound and calcium carbide to the mass of the stainless steel ball beads is 1:30 to 1:100 (1: 30 to 100)).
In the invention, the volume of the absolute ethyl alcohol is 8-15% of the volume of the ball milling tank.
The rhombic hole graphite single alkyne derivative prepared by the method has excellent electrochemical performance, and can be used for preparing negative electrode materials of lithium ion batteries, sodium ion batteries and potassium ion batteries.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of a rhombic pore graphite single alkyne derivative, wherein b corresponds to the product of example 1, c corresponds to the product of example 2, and d corresponds to the product of example 3.
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 50mA g-1The voltage range is 0.01 to 3.0V (vs. Li/Li)+)。
FIG. 4 is a graph of cycle performance of the product of example 1 of the present invention as a negative electrode material for a lithium ion battery. The charge-discharge current density is 50mA g-1The voltage range is 0.01 to 3.0V (vs. Li/Li)+)。
Figure 5 is an XRD pattern of the product of example 2 of the invention.
Fig. 6 shows 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)+)。
Figure 7 is an XRD pattern of the product of example 3 of the invention.
Fig. 8 is 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
1.18 g of 1,2,4, 5-tetrachlorobenzene and 2.82 g of calcium carbide are weighed, dispersed in 15 ml of absolute ethyl alcohol, transferred to a stainless steel ball milling tank with the volume of 100 ml (matched with 150 g of stainless steel ball milling beads), vacuumized, filled with high-purity argon and sealed; 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 4 hours at 550 ℃ under the protection of high-purity 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 rhombic porous graphite monoalkyne derivative (FIG. 1 b). The matching of the X-ray diffraction peak position shown in FIG. 2 with the characteristic peak position of graphite (standard card No. 65-6212) indicates that the rhombic pore graphite mono-alkyne derivative is a partially graphitized carbon material containing a small amount of silicon carbide (from calcium carbide raw material) impurities.
Weighing the diamond-shaped hole graphite single alkyne derivative, Super P conductive carbon and polyvinylidene fluoride binder according to the mass ratio of 8:1:1, dispersing 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 cells of the CR2016 type were assembled in a glove box filled with argon, with lithium metal as the 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 50mAg-1The voltage range is 0.01 to 3.0V (vs. Li/Li)+). FIG. 3 is the potential curves of the first and second circles of charge and discharge processes, the specific discharge and charge capacities of the first circle are 938 and 395mAhg respectively-1Corresponding to 42% of coulombic efficiency, irreversible capacity comes from an SEI film generated on the surface of the electrode and an irreversible lithium intercalation site; the charging specific capacity of the second ring is 385 mAhg-1Coulomb efficiency increased to 88%. FIG. 4 is a graph showing the cycle performance at this current density, and the reversible capacity after 40 cycles of charge and discharge is 363 mAh g-1The capacity retention rate with respect to the second turn was 94%.
Example 2
1.19 g of 1,2,4, 5-tetrachloropyridine and 2.81 g of calcium carbide are weighed, dispersed in 15 ml of absolute ethyl alcohol, transferred to a stainless steel ball milling tank with the volume of 100 ml (matched with 150 g of stainless steel ball milling beads), vacuumized, filled with high-purity argon and sealed; 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 18 hours; annealing the ball-milled product for 3 hours at the temperature of 600 ℃ under the protection of high-purity 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 rhombic porous graphite monoalkyne derivative (FIG. 1 c). The XRD pattern (fig. 5) shows that the rhombic pore graphite monoalkyne derivative is a partially graphitized carbon material containing a small amount of silicon carbide impurities.
Weighing the diamond-shaped hole graphite single alkyne derivative, Super P conductive carbon and polyvinylidene fluoride binder according to the mass ratio of 8:1:1, and dividingDispersing in 1-methyl-2-pyrrolidone solvent, uniformly coating the slurry on copper foil, vacuum drying at 80 deg.C for 12 hr, and cutting into 14 mm diameter wafer as 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. 6 is the potential curves of the first and second circles of charging and discharging processes, the first circle of discharging and charging specific capacities are 824 and 239mAhg respectively-1The irreversible capacity comes from an SEI film generated on the surface of the electrode and an irreversible sodium storage site, and the reversible specific capacity of the second circle is 218 mAhg-1Corresponding to an increase in coulomb efficiency of 82%.
Example 3
Weighing 0.64 g of pyrazine and 4.10 g of calcium carbide, dispersing in 20 ml of absolute ethyl alcohol, transferring to a stainless steel ball milling tank (provided with 375 g of stainless steel balls) with the volume of 250 ml, vacuumizing, filling high-purity 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 24 hours; annealing the ball-milled product for 5 hours at 400 ℃ under the protection of high-purity argon; the annealed product was rinsed three times in 0.15 mol/l nitric acid solution; vacuum drying at 60 deg.C for 24 hr to obtain rhombic porous graphite monoalkyne derivative (FIG. 1 d). The XRD pattern (fig. 7) shows that the rhombic pore graphite monoalkyne derivative is a partially graphitized carbon material containing a small amount of silicon carbide impurities.
Weighing the diamond-shaped hole graphite single alkyne derivative, Super P conductive carbon and polyvinylidene fluoride binder according to the mass ratio of 8:1:1, dispersing 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 (E)C/PC (polycarbonate), the volume ratio of which is 1: 1), is used as an electrolyte, and glassy carbon fiber GF/F is used as a 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. 8 is a potential curve of the first and second cycles of charge and discharge processes, the first cycle of discharge and charge specific capacities being 453 and 146mAhg, 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 132 mAhg-1Corresponding to a coulombic efficiency of 71%.
Claims (7)
1. The rhombic hole graphite single alkyne derivative is characterized in that the molecular structure is as follows: two ends of the ethynyl are respectively connected with 1,2,4, 5-sites or 2,3,5, 6-sites of adjacent six-membered conjugated cyclic compounds to form an ordered close-packed approximate rhombic pore structure consisting of 18 atoms.
2. A preparation method of a rhombic hole graphite single alkyne derivative is characterized by comprising the following specific steps:
(1) dispersing a certain amount of hexahydric conjugated cyclic compound with specific substitution sites and calcium carbide in absolute ethyl alcohol, transferring the solution to a stainless steel ball milling tank, vacuumizing, filling argon, and sealing;
(2) placing the ball milling tank in a planetary ball mill, and operating at the speed of 500-600 revolutions per minute for 12-24 hours;
(3) annealing the ball-milled product for 3-5 hours at the temperature of 400-600 ℃ under the protection of argon;
(4) immersing and washing the annealing product in a nitric acid solution of 0.1-0.15 mol/L for 2-4 times;
(5) and (3) drying the mixture in vacuum at the temperature of between 60 and 80 ℃ for 12 to 24 hours to obtain the rhombic porous graphite monoalkyne derivative.
3. The method of preparing a rhombic pore graphite single alkyne derivative as claimed in claim 2, wherein the six-membered conjugated cyclic compound having a specific substitution site comprises one or more of 1,2,4, 5-tetrachlorobenzene, 1,2,4, 5-tetrabromobenzene, 1,2,4, 5-tetraiodobenzene, 2,3,5, 6-tetrachloropyridine, 2,3,5, 6-tetrabromopyridine, 2,3,5, 6-tetraiodopyridine, pyrazine, 2,3,5, 6-tetrachloropyrazine, 2,3,5, 6-tetrabromopyrazine, 2,3,5, 6-tetraiodopyrazine.
4. The preparation method of the rhombic pore graphite single alkyne derivative according to claim 3, wherein the molar ratio of the six-membered conjugated cyclic compound to the calcium carbide is 1 (2-10).
5. The preparation method of the rhombic pore graphite single alkyne derivative according to claim 4, wherein the ratio of the total mass of the six-membered conjugated cyclic compound and the calcium carbide to the mass of the stainless steel beads is 1 (30-100).
6. The preparation method of the rhombic bore graphite mono-alkyne derivative as claimed in claim 4, wherein the volume of the absolute ethyl alcohol is 8-15% of the volume of the ball milling tank.
7. The use of the rhombohedral pore graphite single alkyne derivative of claim 1 in the preparation of negative electrode materials of lithium ion batteries, sodium ion batteries and potassium ion batteries.
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Cited By (2)
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| CN113745479A (en) * | 2021-08-26 | 2021-12-03 | 复旦大学 | Lithium ion battery cathode material with wide temperature zone excellent performance and preparation method thereof |
| CN114308026A (en) * | 2021-12-07 | 2022-04-12 | 天津理工大学 | Graphite alkynyl diatomic catalyst and preparation method and application thereof |
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