CN115490213A - Metal organic framework derived VSe 2 Material, preparation method and application thereof - Google Patents
Metal organic framework derived VSe 2 Material, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of battery cathode materials, and discloses metal organic framework derived VSe 2 A material and a preparation method and application thereof. The method comprises the following steps: carrying out heat treatment on the metal organic framework containing the V element and selenium powder in an inert atmosphere to obtain the VSe 2 A material; wherein the mass ratio of the metal organic framework material to the selenium powder is 1:2-15 ℃, and the heat treatment temperature is 400-550 ℃. Metal organic framework-derived VSe provided in the invention 2 The preparation method of the material has simple process and mild condition, and gold is obtained by preparationVSe derived from organic frameworks 2 The material has excellent electrochemical performance and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of battery cathode materials, in particular to metal organic framework derived VSe 2 A material and a preparation method and application thereof.
Background
VSe 2 Being a member of the large family of selenides of vanadium, is a typical layered structure (in which vanadium layers are alternately positioned between two selenium layers, forming a sandwich structure stacked by van der waals interactions), electrical conductivity (1.0 × 10) 3 S·m -1 ) Above VS 2 (9.9S·m -1 ) And the like. In addition, the electronegativity of Se is smaller than that of oxygen and sulfur, resulting in a decrease in the ion mobility barrier of selenide. More importantly, vanadium diselenide has a large interlayer spacing
Which can provide sufficient transport channels and active sites for ions. Therefore, VSe 2 Are potential candidates for negative electrode materials for lithium/sodium ion batteries. However, similar to most transition metal sulfides, VSe 2 The electrode material also has the problems of volume expansion, slow reaction kinetics and the like in the circulation process, so that the electrochemical circulation stability is poor.
To improve VSe 2 Many studies on the properties of materials have been made. CN109279584B discloses a self-assembling VSe 2 A synthesis method of a nanosheet, 1) pretreating carbon cloth; 2) Weighing selenourea and a vanadium source, dissolving the selenourea and the vanadium source in 30mL of solution, uniformly stirring by magnetic force, and then putting treated Carbon Cloth (CC) into the solution to obtain mixed solution; 3) Transferring the mixed solution obtained in the step 2) to a 50mL high-temperature high-pressure reaction kettle with a para-polyphenyl lining, then adding an ammonium fluoride morphology regulating agent into the reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven for hydrothermal reaction; naturally cooling to room temperature, taking out the carbon cloth, washing, and vacuum drying to obtain the self-assembled VSe 2 the/CC nano-sheet array self-supporting electrode. The hydrothermal method adopted by the method has the characteristics of simple process, short preparation period and easily controlled reaction conditions, and the prepared self-assemblyVSe 2 The nano-sheet can accelerate the electron transfer rate. However, VSe synthesized by this method 2 The application of the/CC nano sheet in the field of batteries is to be explored.
CN110137460B preparation of precursor MIL-47 (BDC) by hydrothermal reaction technique n+ Then synthesizing V by high-temperature gas-phase sulfurization technology 3 S 4 @ C hollow nanotube. The method comprises the following steps: adding a vanadium source, cetyl trimethyl ammonium bromide, ascorbic acid and terephthalic acid into water, stirring, carrying out hydrothermal treatment to form a mixed solution with a precursor, carrying out suction filtration on the mixed solution, drying to form yellow-green powder, adding thioacetamide, carrying out gas-phase vulcanization in a tubular furnace to generate hollow tubular V 3 S 4 @ C nanocomposites. V prepared by the method 3 S 4 Compared with other vanadium sulfide carbon-based composite materials, the number of active sites and the structural stability of the @ C nano composite material are obviously improved, and the composite material has great advantages in the aspect of electrochemical energy storage. However, this method is directed to the preparation of VSe 2 The ratio of vanadium source to selenium source in the process is to be further studied.
The metal organic framework is a novel crystal material with a periodic network structure and is formed by a self-assembly process of metal ions and organic ligands. In emerging electrode materials, the metal organic framework has the obvious advantages of large specific surface area, controllable aperture, low density, good thermal stability, ordered crystal structure and the like, and can be directly used as electrode materials of batteries and super capacitors. However, metal-organic frameworks tend to have lower electrical conductivity and poorer stability, which limits their energy storage and conversion efficiency.
Therefore, it is highly desirable to provide a method for preparing VSe using a metal organic framework 2 The method of (1).
Disclosure of Invention
The invention aims to overcome the problem of poor electrochemical cycling stability of a vanadium diselenide material in the prior art, and provides VSe derived from a metal organic framework 2 A material, a preparation method and application thereof.
To achieve the above object, a first aspect of the present invention providesMetal organic framework derived VSe 2 A method of preparing a material, the method comprising: carrying out heat treatment on the metal organic framework containing the V element and selenium powder in an inert atmosphere to obtain the VSe 2 A material; wherein the mass ratio of the metal organic framework material to the selenium powder is 1:2-15 ℃, and the heat treatment temperature is 400-550 ℃.
A second aspect of the invention provides a metal organic framework-derived VSe prepared by the method of the first aspect of the invention 2 A material.
In a third aspect, the invention provides a VSe prepared by a process according to the first aspect of the invention 2 The use of the material in batteries, preferably as electrode material in lithium ion batteries or sodium ion batteries.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
1) The metal organic framework-derived VSe provided in the present invention 2 The preparation method of the material has simple process and mild condition, and is suitable for large-scale production;
2) The metal organic framework-derived VSe provided in the present invention 2 When the material is used as a negative electrode material of a lithium ion battery and a sodium ion battery, the contact between an electrode and electrolyte can be improved, the volume/structure change of the electrode material can be relieved, the improvement of lithium/sodium storage performance is facilitated, and the material has excellent electrochemical performance.
Drawings
FIG. 1 is a metal organic framework-derived VSe prepared in example 1 2 XRD characterization pattern of the material;
FIG. 2 is a metal organic framework-derived VSe prepared in example 2 2 XRD characterization pattern of the material;
FIG. 3 is an XRD characterization of the metal organic framework-derived materials prepared in comparative examples 1-2;
FIG. 4 is a XRD characterization of the materials prepared in comparative examples 3-5;
FIG. 5 is a metal organic framework-derived VSe prepared in example 1 2 Scanning electron micrographs of the material;
FIG. 6 is a metal organic framework-derived VSe prepared in example 2 2 Scanning electron micrographs of the material;
FIG. 7 is a metal organic framework-derived VSe prepared in example 1 and example 2 2 Adsorption/desorption isotherm plot of the material;
FIG. 8 is a metal organic framework-derived VSe prepared in example 1 and example 2 2 Pore size distribution curve graph of the material;
FIG. 9 is a VSe derived from the metal-organic framework prepared in example 1 2 A constant current cycle performance diagram of the lithium ion battery is obtained by material preparation;
FIG. 10 is a VSe derived from a metal-organic framework prepared in example 1 2 A multiplying power cycle performance diagram of the lithium ion battery obtained by material preparation;
FIG. 11 is a scheme showing the use of VSe derived from the metal-organic framework prepared in example 1 2 A constant-current cycle performance diagram of the sodium-ion battery obtained by material preparation;
FIG. 12 is a VSe derived from the metal-organic framework prepared in example 1 2 A multiplying power cycle performance diagram of the sodium-ion battery obtained by material preparation;
FIG. 13 is a VSe derived from a metal organic framework prepared in example 2 2 Preparing a constant-current cycle performance diagram of the lithium ion battery by using the material;
FIG. 14 is a VSe derived from the metal organic framework prepared in example 2 2 A multiplying power cycle performance diagram of the lithium ion battery is obtained by material preparation;
FIG. 15 is a VSe derived from the metal organic framework prepared in example 2 2 A constant-current cycle performance diagram of the sodium-ion battery obtained by material preparation;
FIG. 16 is a VSe derived from the metal organic framework prepared in example 2 2 The multiplying power cycle performance diagram of the sodium ion battery prepared from the material is shown.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect of the invention there is provided a metal organic framework derived VSe 2 A method of preparing a material, the method comprising: carrying out heat treatment on the metal organic framework containing the V element and selenium powder in an inert atmosphere to obtain the VSe 2 A material;
wherein the mass ratio of the metal organic framework material to the selenium powder is 1:2-15 ℃, and the heat treatment temperature is 400-550 ℃.
In a preferred embodiment, the metal-organic framework material comprises MIL-47 (V) and/or MIL-101 (V); preferably, the metal organic framework material is MIL-47 (V) or MIL-101 (V).
In a preferred embodiment, the method for preparing MIL-47 (V) comprises: vanadium pentoxide (V) 2 O 5 ) And terephthalic acid and ascorbic acid are mixed in a solvent I, and hydrothermal reaction-I is carried out at 170-190 ℃ to obtain the MIL-47 (V).
In a preferred embodiment, the solvent I is water.
In a preferred embodiment, the molar ratio of vanadium pentoxide to terephthalic acid to ascorbic acid is 1:7-10:0.5-3.5, preferably 1:8-9:1.5-2.5.
In a preferred embodiment, the ratio of the amount of vanadium pentoxide to solvent I is 1mmol:50-110mL, preferably 1mmol:70-90mL.
In a preferred embodiment, the reaction temperature of the hydrothermal reaction-I is 175 to 185 ℃.
In a preferred embodiment, the reaction time of the hydrothermal reaction-I is 8 to 16h, preferably 10 to 14h.
In a preferred embodiment, after the hydrothermal reaction-I reaction is completed, filtering, washing and drying are performed to obtain the MIL-47 (V).
In a preferred embodiment, the method for preparing MIL-101 (V) comprises: vanadium trichloride (VCl) is firstly 3 ) And dissolving terephthalic acid in a solvent II, carrying out hydrothermal reaction-II at 110-130 ℃ to obtain an intermediate product, and then putting the intermediate product in an N, N-dimethylformamide solution for heating treatment under the protection of inert gas to obtain the MIL-101 (V).
In a preferred embodiment, the solvent II is water and/or an alcoholic solvent, preferably water or ethanol.
In a preferred embodiment, the molar ratio of vanadium trichloride to terephthalic acid is 1:0.8 to 2, preferably 1:1-1.5.
In a preferred embodiment, the ratio of the amount of vanadium trichloride to solvent II is 1mmol:1-10mL, preferably 1mmol:4-6mL.
In a preferred embodiment, the dissolution is carried out under ultrasound and stirring. Wherein, in the invention, the mixing of the vanadium trichloride and the terephthalic acid can be promoted by ultrasonic and stirring.
In a preferred embodiment, the reaction temperature of the hydrothermal reaction-II is 115 to 125 ℃.
In a preferred embodiment, the reaction time of the hydrothermal reaction-II is 35 to 55 hours, preferably 40 to 50 hours.
In a preferred embodiment, after the hydrothermal reaction-II reaction is finished, centrifugation and washing are performed to obtain the intermediate product.
In a preferred embodiment, the present invention does not specifically limit the amounts of the intermediate product and the N, N-dimethylformamide solution as long as the intermediate product is immersed in the N, N-dimethylformamide solution.
In a preferred embodiment, the heat treatment is carried out with stirring, the heat treatment temperature being between 60 and 80 ℃, preferably between 65 and 75 ℃.
In a preferred embodiment, after the heat treatment is completed, centrifugation, washing and drying are performed to obtain the MIL-101 (V).
Wherein, the invention does not specially limit the ultrasonic treatment, the stirring, the filtering, the washing and the drying, and the operation is carried out according to the routine operation in the field.
In a preferred embodiment, the mass ratio of the metal-organic framework material to the selenium powder is 1:8-12, wherein the heat treatment temperature is 450-550 ℃.
In a preferred embodiment, the inert gas is selected from at least one of nitrogen and argon, preferably nitrogen.
In a preferred embodiment, the heat treatment conditions further include: the heating rate is 1-5 ℃/min, preferably 1-3 ℃/min; the heat treatment time is 1-5h, preferably 2-4h.
In a preferred embodiment, the heat treatment is carried out in a tube furnace, wherein the metal-organic framework material and the selenium powder are placed at intervals, and the selenium powder is located upstream of the tube furnace.
A second aspect of the invention provides a metal organic framework-derived VSe prepared by the method of the first aspect of the invention 2 A material.
In a third aspect, the invention provides a VSe prepared by the method of the first aspect of the invention 2 The use of the material in batteries, preferably as electrode material in lithium ion batteries or sodium ion batteries.
The present invention will be described in detail below by way of examples.
Preparation of MIL-47 (V): 0.75mmol of vanadium pentoxide (V) 2 O 5 ) 6.3mmol of terephthalic acid (H) 2 BDC) and 1.5mmol ascorbic acid are mixed in 60mL water, heated and stirred at 45 ℃ for 3h, then transferred to an autoclave with a polytetrafluoroethylene lining, subjected to hydrothermal reaction-I at 180 ℃, cooled to room temperature after 12h of reaction, filtered, washed with deionized water and absolute ethyl alcohol for multiple times respectively, and dried under vacuum at 80 ℃ for 12h to obtain MIL-47 (V).
Preparation of MIL-101 (V): 10mmol of vanadium trichloride (VCl) 3 ) And 10mmol terephthalic acid (H) 2 BDC) is dissolved in 50mL of water, the mixture is stirred for 1 hour, then is subjected to ultrasonic treatment for 30 minutes, then is transferred to a high-pressure reaction kettle with a polytetrafluoroethylene lining, is subjected to hydrothermal reaction-II at 120 ℃, is cooled to room temperature after being subjected to reaction for 48 hours, is subjected to centrifugal separation at the rotating speed of 4000 revolutions per minute, and is washed for multiple times by deionized water and absolute ethyl alcohol to obtain a green intermediate product; and then placing the green intermediate product in an N, N-dimethylformamide solution, heating to 70 ℃ under the protection of nitrogen gas, stirring for 3h, carrying out centrifugal cleaning at the rotating speed of 8000 rpm, and carrying out vacuum drying at 120 ℃ for 24h to obtain MIL-101 (V).
Example 1
Placing 0.2g of metal organic framework MIL-47 (V) and 2g of selenium powder in a tube furnace at intervals, introducing nitrogen into the tube furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 3h to obtain metal organic framework-derived VSe 2 A material.
Example 2
Placing 0.2g of metal organic framework MIL-101 (V) and 2g of selenium powder in a tube furnace at intervals, introducing nitrogen into the tube furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 3h to obtain metal organic framework-derived VSe 2 A material.
Comparative example 1
And (2) placing 0.1g of metal organic framework MIL-47 (V) and 2g of selenium powder in a tube furnace at intervals, introducing nitrogen into the tube furnace, heating to 500 ℃ at the heating rate of 2 ℃/min, and preserving heat for 3h to obtain the metal organic framework derivative material.
Comparative example 2
And (2) placing 0.2g of metal organic framework MIL-47 (V) and 2g of selenium powder in a tube furnace at intervals, introducing nitrogen into the upstream of the tube furnace, heating to 400 ℃ at the heating rate of 2 ℃/min, and preserving heat for 3h to obtain the metal organic framework derivative material.
Comparative example 3
0.2g of ammonium metavanadate (NH) 4 VO 3 ) And 2g of selenium powder are placed in a tube furnace at intervals, the selenium powder is positioned at the upstream of the tube furnace, nitrogen is introduced, and the temperature is controlled at 2 ℃/minThe temperature is raised to 500 ℃ at the heating rate, and the temperature is kept for 3 hours to obtain the material.
Comparative example 4
0.2g of vanadium pentoxide (V) 2 O 5 ) And 2g of selenium powder are placed in a tube furnace at intervals, the selenium powder is positioned at the upstream of the tube furnace, nitrogen is introduced, the temperature is raised to 500 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 3 hours, so that the material is obtained.
Comparative example 5
0.2g of vanadyl (C) acetylacetonate 10 H 4 O 5 V) and 2g of selenium powder are placed in a tube furnace at intervals, the selenium powder is positioned at the upstream of the tube furnace, nitrogen is introduced, the temperature is raised to 500 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 3h, so that the material is obtained.
Test example 1
VSe derived from the metal organic framework prepared in example 1-2 2 The material was subjected to XRD characterization, and the characterization results are shown in fig. 1 and fig. 2, respectively. The XRD characterization of the materials prepared in comparative examples 1-5 was performed, and the results are shown in FIGS. 3a, 3b, 4a, 4b, and 4c, respectively.
As can be seen from fig. 1 and 2, the metal-organic framework-derived vses prepared in example 1 and example 2 2 Diffraction peaks of the Material and Standard card VSe 2 (JCPDS card numbers 89-1641) are matched consistently, which shows that the method of the invention can be used for obtaining high-purity VSe 2 A material.
As can be seen from FIG. 3a, the material derived from the metal-organic framework prepared in comparative example 1 and V 2 O 3 (JCPDS card number 34-0187) is matched consistently, which indicates that excessive selenium powder reacts with metal organic framework MIL-47 (V) to obtain V 2 O 3 . As can be seen from FIG. 3b, when the heat treatment temperature is relatively low (400 ℃ C.), the resulting metal-organic framework-derived VSe is prepared 2 The material contains impurities and has low purity.
As can be seen from FIGS. 4a to 4c, the diffraction peaks and the standard V Se of the materials obtained when ammonium metavanadate, vanadium pentoxide and vanadyl acetylacetonate are respectively used as the vanadium source 2 (JCPDS card numbers 89-1641) are not matched, that is, under the same conditions, ammonium metavanadate, vanadium pentoxide and acetylacetonatooxygen are selectedVanadium as vanadium source can not synthesize VSe 2 。
Test example 2
The metal organic frameworks derived VSe prepared in example 1 and example 2 were subjected to 2 The material was characterized by scanning electron microscopy, and the characterization results are shown in fig. 5 and 6, respectively.
As can be seen from FIG. 5, the metal-organic framework-derived VSe prepared in example 1 2 The material is in a nano rod shape and has uniform appearance. As can be seen from FIG. 6, the metal-organic framework-derived VSe prepared in example 2 2 The material is irregular nano-bulk particles.
When the metal-organic framework is derivatized 2 When the nano-rod-shaped structure or the nano-bulk particles are used as the negative electrode of a lithium ion or sodium ion battery, the nano-rod-shaped structure or the nano-bulk particles can shorten the transmission distance of lithium ions or sodium ions and effectively improve VSe 2 Electrochemical performance of the electrode material in a lithium-ion or sodium-ion battery.
Test example 3
The metal organic frameworks derived VSe prepared in example 1 and example 2 were subjected to 2 The material was subjected to adsorption/desorption characterization, and the characterization results are shown in fig. 7 and fig. 8, respectively. Wherein, FIG. 7 shows the metal organic framework-derived VSe prepared in example 1 and example 2 2 Adsorption/desorption isotherms of the materials, fig. 8 is a graph of metal organic framework-derived VSe prepared in example 1 and example 2 2 Pore size distribution curve of the material.
As can be seen from FIGS. 7 and 8, VSe derived from the metal-organic framework prepared in example 1 2 The material presents a typical IV-type adsorption curve, is a mesoporous material and has a specific surface area of 148m 2 ·g -1 The average pore diameter was 4.8nm. Metal organic framework-derived VSe prepared in example 2 2 The material presents a typical IV-type adsorption curve, is a mesoporous material and has a specific surface area of 73m 2 ·g -1 The average pore diameter was 3.4nm.
Wherein the metal-organic framework is derived from VSe 2 The porous structure of the material provides abundant space for the storage of lithium ions or sodium ions, and can buffer the electrode material in the circulation processThe volume expansion and other problems occur, and the high-performance lithium ion or sodium ion battery is obtained.
Test example 4
VSe derived from the metal-organic framework prepared in example 1 2 The material is prepared into the lithium ion battery, and the specific preparation method comprises the following steps:
will VSe 2 Materials, carboxymethyl cellulose and Super P conductive carbon black were as follows 8:1:1 in a mass ratio of H 2 And mixing the materials in the mixture O, and fully grinding the mixture to obtain slurry. Subsequently, it was uniformly covered on a copper foil by a coater and dried in a vacuum drying oven at 110 ℃ for 12 hours. Then cutting the copper foil to a pole piece with a diameter of 14mm, and cutting the copper foil to obtain an active substance (VSe) 2 Material) had a mass of about 1.2mg. The metal lithium is used as a reference electrode and a counter electrode, whatman GF/D is used as a diaphragm, and the CR2032 button cell is assembled in a glove box with water and oxygen contents of less than 0.5 ppm. The lithium ion electrolyte comprises 1M lithium hexafluorophosphate dissolved in ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in the mass ratio of 1: 1.
The lithium ion battery constant current cycle performance test (current density of 0.1A/g and voltage of 0.001-3.0V) is carried out on the lithium ion battery by a blue battery tester CT2001A, and the test result is shown in figure 9. As can be seen from FIG. 9, the first coulombic efficiency of the lithium ion battery is 62.7%, the current density is 0.1A/g, and the discharge specific capacity is 785mAh/g after 50 cycles.
The lithium ion battery multiplying power cycle performance test (voltage of 0.001-3.0V) is carried out on the lithium ion battery by a blue battery tester CT2001A, and the test result is shown in figure 10. As can be seen from FIG. 10, the reversible specific capacities at current densities of 0.1, 0.2, 0.5, 1, 2 and 5A/g reached 904.9, 760.0, 687.7, 634.2, 569.7 and 476.4mAh/g, respectively. In addition, when the current density was restored to 0.1, 0.2, 0.5, 1 and 2A/g, reversible specific capacities of 914.4, 847.4, 766.2, 710.4 and 651.6mAh/g could be obtained. It is noted that after charging and discharging at different current densities (after 110 cycles), VSe 2 The electrode can still maintain stable charge-discharge specific capacity, and the electrode has excellent electrochemical performance as a lithium ion negative electrode material.
Test example 5
The metal-organic framework-derived VSe prepared in example 1 was synthesized according to the method of test example 4 2 The material is prepared into a sodium ion battery, and the difference is that metal sodium is used as a reference electrode and a counter electrode, and sodium perchlorate with the electrolyte component of 1M is dissolved in propylene carbonate and ethylene carbonate with the mass ratio of 1.
The sodium ion battery was subjected to constant current cycle performance test and rate cycle performance test according to the method in test example 4, and the test results are shown in fig. 11 and 12.
As can be seen from FIG. 11, after 50 cycles, it can provide a reversible specific capacity of 288.8 mAh/g. As can be seen from FIG. 12, the reversible specific capacities at current densities of 0.1, 0.2, 0.5, 1, 2 and 5A/g reached 389.5, 294.7, 207.8, 145.7, 105.1 and 80.6mAh/g, respectively. In addition, when the current density was restored to 0.1, 0.2, 0.5, 1 and 2A/g, reversible specific capacities of 332.1, 251.5, 155.5, 106.1 and 75.1mAh/g could be obtained. The above results illustrate VSe 2 The material has excellent sodium ion storage performance.
Test example 6
The metal-organic framework-derived VSe prepared in example 2 was subjected to the same procedure as in test example 4 2 The lithium ion battery prepared from the material was subjected to constant current cycle performance test and rate cycle performance test according to the method in test example 4, and the test results are shown in fig. 13 and 14.
As can be seen from FIG. 13, the initial coulombic efficiency was 62.5%, the current density was 0.1A/g, and the specific discharge capacity was 755mAh/g after 50 cycles. As can be seen from FIG. 14, the reversible specific capacities at current densities of 0.1, 0.2, 0.5, 1, 2 and 5A/g were 776.6, 688.3, 638.3, 590, 531.4 and 438.6mAh/g, respectively. In addition, reversible specific capacities of 768.3, 762.4, 686.5, 643 and 569.7mAh/g were obtained when the current densities were restored to 0.1, 0.2, 0.5, 1 and 2A/g. It is noted that VSe after charging and discharging at different current densities (after 110 cycles) 2 The electrode can still keep stable charge-discharge specific capacity, and the electrode has better electrochemical performance when being used as a lithium ion negative electrode material.
Test example 7
Same as in test example 5 except that the metal-organic framework-derived VSe prepared in example 2 was subjected to 2 The material was prepared into a sodium ion battery, and the sodium ion battery was subjected to constant current cycle performance test and rate cycle performance test according to the method in test example 4, and the test results are shown in fig. 15 and 16.
As can be seen from FIG. 15, after 50 cycles, it can provide a reversible specific capacity of 224.1 mAh/g. As can be seen from FIG. 16, the reversible specific capacities at current densities of 0.1, 0.2, 0.5, 1, 2 and 5A/g reached 264.2, 229.9, 175.6, 137.7, 107.6 and 81.9mAh/g, respectively. In addition, reversible specific capacities of 231.3, 201.9, 151.8, 121.1 and 96mAh/g were obtained when the current density was restored to 0.1, 0.2, 0.5, 1 and 2A/g.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. Metal organic framework derived VSe 2 A method of preparing a material, the method comprising: carrying out heat treatment on the metal organic framework material containing the V element and selenium powder in an inert atmosphere to obtain the VSe 2 A material;
wherein the mass ratio of the metal organic framework material to the selenium powder is 1:2-15 ℃, and the heat treatment temperature is 400-550 ℃.
2. The preparation method according to claim 1, wherein the metal-organic framework material comprises MIL-47 (V) and/or MIL-101 (V);
preferably, the metal organic framework material is MIL-47 (V) or MIL-101 (V).
3. The method of claim 2, wherein the method of preparing MIL-47 (V) comprises: mixing vanadium pentoxide, terephthalic acid and ascorbic acid in a solvent I, and carrying out hydrothermal reaction-I at 170-190 ℃ to obtain the MIL-47 (V).
4. The production method according to claim 3, wherein the molar ratio of vanadium pentoxide to terephthalic acid to ascorbic acid is 1:7-10:0.5-3.5, preferably 1:8-9:1.5-2.5;
preferably, the dosage ratio of the vanadium pentoxide to the solvent I is 1mmol:50-110mL, preferably 1mmol:70-90mL;
preferably, the reaction temperature of the hydrothermal reaction-I is 175-185 ℃;
preferably, the reaction time of the hydrothermal reaction-I is 8-16h, preferably 10-14h.
5. The method of claim 2, wherein the method of preparing MIL-101 (V) comprises: dissolving vanadium trichloride and terephthalic acid in a solvent II, carrying out hydrothermal reaction-II at 110-130 ℃ to obtain an intermediate product, and then placing the intermediate product in an N, N-dimethylformamide solution under the protection of inert gas for heating treatment to obtain the MIL-101 (V).
6. The production process according to claim 5, wherein the molar ratio of vanadium trichloride to terephthalic acid is 1:0.8 to 2, preferably 1:1-1.5;
preferably, the ratio of the amount of vanadium trichloride to the amount of solvent II is 1mmol:1-10mL, preferably 1mmol:4-6mL;
preferably, the reaction temperature of the hydrothermal reaction-II is 115-125 ℃.
Preferably, the reaction time of the hydrothermal reaction-II is 35 to 55 hours, preferably 40 to 50 hours.
7. The process according to claim 5 or 6, wherein the heat treatment is carried out under stirring at a temperature of from 60 to 80 ℃, preferably from 65 to 75 ℃.
8. The production method according to any one of claims 1 to 7, wherein the mass ratio of the metal-organic framework material to the selenium powder is 1:8-12, wherein the heat treatment temperature is 450-550 ℃;
preferably, the conditions of the heat treatment further include: the heating rate is 1-5 ℃/min, preferably 1-3 ℃/min; the heat treatment time is 1-5h, preferably 2-4h.
9. A metal organic framework-derived VSe prepared by the process of any one of claims 1-8 2 A material.
10. The VSe of claim 9 2 The use of the material in batteries, preferably as electrode material in lithium ion batteries or sodium ion batteries.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191778A (en) * | 2013-02-28 | 2013-07-10 | 北京化工大学常州先进材料研究院 | Preparation method of metal organic framework loaded Pt-base catalyst |
| CN106076421A (en) * | 2016-06-14 | 2016-11-09 | 华东师范大学 | A kind of MIL 53 (Fe)/g C3n4the preparation method of nanometer sheet composite photocatalyst material |
| CN108767247A (en) * | 2018-07-02 | 2018-11-06 | 南京工业大学 | A kind of carbon based metal organic frame MOF compound derived material preparation methods and application |
| WO2019050473A1 (en) * | 2017-09-08 | 2019-03-14 | National University Of Singapore | Vanadium-based metal-organic frameworks and a method of producing the same |
| CN109935810A (en) * | 2019-03-07 | 2019-06-25 | 肇庆市华师大光电产业研究院 | A kind of preparation method of anode material of lithium-ion battery |
| CN110137460A (en) * | 2019-05-09 | 2019-08-16 | 济南大学 | A kind of hollow V of lithium/sodium ions to potassium ions battery3S4The preparation method of@C nano pipe negative electrode material |
| CN111440326A (en) * | 2020-03-20 | 2020-07-24 | 西南大学 | Nanoscale MI L-47 (V) metal organic framework compound and preparation method thereof |
| CN112442674A (en) * | 2019-09-03 | 2021-03-05 | Asm Ip私人控股有限公司 | Method and apparatus for depositing chalcogenide films and structures including films |
| US20210167387A1 (en) * | 2018-08-07 | 2021-06-03 | Shanghai Zijian Chemical Technology Co., Ltd | Vanadium sodium phosphate positive electrode material, sodium ion battery, preparation method therefor, and use thereof |
| CN113277484A (en) * | 2020-02-19 | 2021-08-20 | 松山湖材料实验室 | High-performance alkaline zinc battery cathode material and preparation method thereof |
| CN113583246A (en) * | 2021-07-22 | 2021-11-02 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of metal organic framework MIL-101-V with three-dimensional mesoporous structure |
| WO2021252723A1 (en) * | 2020-06-10 | 2021-12-16 | The Johns Hopkins University | Linker-functionalized metal-organic framework for polysulfide tethering in lithium-sulfur batteries |
| CN114242983A (en) * | 2021-12-20 | 2022-03-25 | 济南大学 | V-shaped groove3S4@ C composite material and preparation method and application thereof |
| CN114702013A (en) * | 2022-03-26 | 2022-07-05 | 北京理工大学 | Sodium ion battery metal selenide negative electrode material and preparation method and application thereof |
-
2022
- 2022-08-30 CN CN202211049050.XA patent/CN115490213B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191778A (en) * | 2013-02-28 | 2013-07-10 | 北京化工大学常州先进材料研究院 | Preparation method of metal organic framework loaded Pt-base catalyst |
| CN106076421A (en) * | 2016-06-14 | 2016-11-09 | 华东师范大学 | A kind of MIL 53 (Fe)/g C3n4the preparation method of nanometer sheet composite photocatalyst material |
| WO2019050473A1 (en) * | 2017-09-08 | 2019-03-14 | National University Of Singapore | Vanadium-based metal-organic frameworks and a method of producing the same |
| CN108767247A (en) * | 2018-07-02 | 2018-11-06 | 南京工业大学 | A kind of carbon based metal organic frame MOF compound derived material preparation methods and application |
| US20210167387A1 (en) * | 2018-08-07 | 2021-06-03 | Shanghai Zijian Chemical Technology Co., Ltd | Vanadium sodium phosphate positive electrode material, sodium ion battery, preparation method therefor, and use thereof |
| CN109935810A (en) * | 2019-03-07 | 2019-06-25 | 肇庆市华师大光电产业研究院 | A kind of preparation method of anode material of lithium-ion battery |
| CN110137460A (en) * | 2019-05-09 | 2019-08-16 | 济南大学 | A kind of hollow V of lithium/sodium ions to potassium ions battery3S4The preparation method of@C nano pipe negative electrode material |
| CN112442674A (en) * | 2019-09-03 | 2021-03-05 | Asm Ip私人控股有限公司 | Method and apparatus for depositing chalcogenide films and structures including films |
| CN113277484A (en) * | 2020-02-19 | 2021-08-20 | 松山湖材料实验室 | High-performance alkaline zinc battery cathode material and preparation method thereof |
| CN111440326A (en) * | 2020-03-20 | 2020-07-24 | 西南大学 | Nanoscale MI L-47 (V) metal organic framework compound and preparation method thereof |
| WO2021252723A1 (en) * | 2020-06-10 | 2021-12-16 | The Johns Hopkins University | Linker-functionalized metal-organic framework for polysulfide tethering in lithium-sulfur batteries |
| CN113583246A (en) * | 2021-07-22 | 2021-11-02 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of metal organic framework MIL-101-V with three-dimensional mesoporous structure |
| CN114242983A (en) * | 2021-12-20 | 2022-03-25 | 济南大学 | V-shaped groove3S4@ C composite material and preparation method and application thereof |
| CN114702013A (en) * | 2022-03-26 | 2022-07-05 | 北京理工大学 | Sodium ion battery metal selenide negative electrode material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| FABIAN CARSON 等: ""Framework Isomerism in Vanadium Metal−Organic Frameworks:MIL-88B(V) and MIL-101(V)"", 《CRYST. GROWTH DES.》, pages 5036 - 5044 * |
| TAIQIANG CHEN 等: "Recent progress on metal–organic frameworkderived materials for sodium-ion battery anodes", 《INORG. CHEM. FRONT.》, pages 567 - 582 * |
| 孙泽航: ""金属有机配位聚合物及衍生硫化物基电极材料构筑和储能性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 014 - 611 * |
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