CN115490213B - VSe derived from metal-organic frameworks 2 Material, preparation method and application thereof - Google Patents
VSe derived from metal-organic frameworks 2 Material, preparation method and application thereof Download PDFInfo
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- CN115490213B CN115490213B CN202211049050.XA CN202211049050A CN115490213B CN 115490213 B CN115490213 B CN 115490213B CN 202211049050 A CN202211049050 A CN 202211049050A CN 115490213 B CN115490213 B CN 115490213B
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- C01B19/00—Selenium; Tellurium; Compounds thereof
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- 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
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Abstract
The invention relates to the technical field of battery cathode materials, and discloses a VSe derivative of a metal-organic framework 2 Materials, and methods of making and using the same. The method comprises the following steps: performing heat treatment on the metal organic framework containing the V element and the selenium powder in an inert atmosphere to obtain VSe 2 A material; wherein, the mass ratio of the metal organic framework material to the selenium powder is 1:2-15, wherein the heat treatment temperature is 400-550 ℃. VSe derived from the metal organic framework provided in the present invention 2 The preparation method of the material has simple process and mild condition, and prepares the VSe derivative by the metal-organic framework 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 VSe derived from a metal-organic framework 2 Materials, and methods of making and using the same.
Background
VSe 2 As a result ofIs a member of the large family of vanadium selenides, a typical layered structure (in which vanadium layers are alternately located between two selenium layers, forming a sandwich structure of van der Waals interaction stacks), conductivity (1.0X10 3 S·m -1 ) Higher than VS 2 (9.9S·m -1 ) And the like. In addition, se is less electronegative than oxygen and sulfur, resulting in a reduction of the ion transport barrier of selenide. More importantly, the vanadium diselenide has larger interlayer spacingWhich is capable of providing sufficient transport channels and active sites for ions. Thus VSe 2 Is a potential candidate for negative electrode materials of lithium/sodium ion batteries. However, like most transition metal sulfides, VSe 2 The electrode material also has problems of volume expansion, slow reaction kinetics and the like in the circulating process, so that the electrochemical circulating stability is poor.
To improve VSe 2 The properties of materials are currently being studied. CN109279584B discloses a self-assembled VSe 2 The synthesis method of the nano-sheet comprises 1) pretreating carbon cloth; 2) Weighing selenourea and vanadium source, dissolving the selenourea and vanadium source in 30mL of solution, magnetically stirring the solution uniformly, and then putting the solution into treated Carbon Cloth (CC) to obtain mixed solution; 3) Transferring the mixed solution obtained in the step 2) into a 50mL high-temperature high-pressure reaction kettle with a para-polyphenyl lining, then adding an ammonium fluoride morphology regulator 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 self-assembled VSe 2 CC nanoplatelet array self-supporting electrode. The hydrothermal method adopted by the method has the characteristics of simple process, short preparation period and easy control of reaction conditions, and the prepared self-assembled VSe 2 The nanoplatelets can accelerate the electron transfer rate. However, VSe synthesized by this method 2 The application of/CC nanoplatelets in the battery field is yet to be explored.
CN110137460B preparation of precursor MIL-47 (BDC) by hydrothermal reaction technique n+ Then synthesizing V by high-temperature gas-phase vulcanization technology 3 S 4 @ C nano hollow tube. Its prescriptionThe method comprises the following steps: mixing vanadium source, cetyl trimethyl ammonium bromide, ascorbic acid and terephthalic acid in water, stirring, performing hydrothermal treatment to obtain mixed solution with precursor, vacuum filtering, oven drying to obtain yellowish green powder, adding thioacetamide, and gas-phase vulcanizing in a tubular furnace to obtain hollow tubular V 3 S 4 @c nanocomposite. V prepared by the method 3 S 4 Compared with other vanadium sulfide carbon-based composite materials, the active site number and the structural stability of the @ C nanocomposite material are obviously improved, and the @ C nanocomposite material has great advantages in the aspect of electrochemical energy storage. However, this method is for preparation 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 self-assembling metal ions and organic ligands. In the 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 the electrode materials of batteries and supercapacitors. However, metal-organic frameworks tend to have lower conductivity and poor stability, which limits their energy storage and conversion efficiency.
Thus, there is a need to provide a method for preparing VSe using metal-organic frameworks 2 Is a method of (2).
Disclosure of Invention
The invention aims to solve 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 Materials, and methods of making and using the same.
To achieve the above object, a first aspect of the present invention provides a metal-organic framework-derived VSe 2 A method of preparing a material, the method comprising: performing heat treatment on the metal organic framework containing the V element and the selenium powder in an inert atmosphere to obtain VSe 2 A material; wherein, the mass ratio of the metal organic framework material to the selenium powder is 1:2-15, wherein the heat treatment temperature is 400-550 ℃.
In a second aspect the invention provides a metal-organic framework derived VSe produced by the process of the first aspect of the invention 2 A material.
A third aspect of the invention provides VSe obtainable by a process according to the first aspect of the invention 2 The use of the material in a battery, preferably as electrode material in a lithium ion battery or a sodium ion battery.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
1) VSe derived from the metal organic framework provided herein 2 The preparation method of the material has simple process and mild condition, and is suitable for large-scale production;
2) VSe derived from the metal organic framework provided herein 2 When the material is used as a negative electrode material of a lithium ion battery or 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 electrochemical performance is excellent.
Drawings
FIG. 1 is a metal organic framework-derived VSe prepared in example 1 2 XRD characterization of the material;
FIG. 2 is a metal organic framework-derived VSe prepared in example 2 2 XRD characterization of the material;
FIG. 3 is an XRD characterization of the metal-organic framework-derived material prepared in comparative examples 1-2;
FIG. 4 is an XRD characterization of the material prepared in comparative examples 3-5;
FIG. 5 is a metal organic framework-derived VSe prepared in example 1 2 Scanning electron microscope images of materials;
FIG. 6 is a metal organic framework-derived VSe prepared in example 2 2 Scanning electron microscope images of materials;
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 example 1 and the practiceVSe derived from the metal organic framework prepared in example 2 2 A pore size distribution graph of the material;
FIG. 9 is a metal organic framework-derived VSe prepared in example 1 2 Constant current cycle performance diagram of lithium ion battery prepared by the material;
FIG. 10 is a metal-organic framework derived VSe prepared in example 1 2 A multiplying power cycle performance diagram of the lithium ion battery prepared by the material;
FIG. 11 is a metal-organic framework-derived VSe prepared in example 1 2 Constant current cycle performance diagram of sodium ion battery prepared by the material;
FIG. 12 is a metal-organic framework-derived VSe prepared in example 1 2 A multiplying power cycle performance diagram of the sodium ion battery prepared by the material;
FIG. 13 is a metal organic framework derived VSe prepared in example 2 2 Constant current cycle performance diagram of lithium ion battery prepared by the material;
FIG. 14 is a metal-organic framework derived VSe prepared in example 2 2 A multiplying power cycle performance diagram of the lithium ion battery prepared by the material;
FIG. 15 is a metal-organic framework derived VSe prepared in example 2 2 Constant current cycle performance diagram of sodium ion battery prepared by the material;
FIG. 16 is a metal organic framework derived VSe using the preparation of example 2 2 And a multiplying power cycle performance diagram of the sodium ion battery prepared by the material.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
A first aspect of the invention provides a metal organic framework-derived VSe 2 A method of preparing a material, the method comprising: performing heat treatment on the metal organic framework containing the V element and the selenium powder in an inert atmosphere to obtain VSe 2 A material;
wherein, the mass ratio of the metal organic framework material to the selenium powder is 1:2-15, wherein 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 MIL-47 (V) is prepared by a process comprising: vanadium pentoxide (V) 2 O 5 ) Mixing terephthalic acid and ascorbic acid in a solvent I, and carrying out hydrothermal reaction-I at 170-190 ℃ to obtain MIL-47 (V).
In a preferred embodiment, the solvent I is water.
In a preferred embodiment, the molar ratio of vanadium pentoxide, terephthalic acid and 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 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 from 175 to 185 ℃.
In a preferred embodiment, the reaction time of the hydrothermal reaction-I is from 8 to 16 hours, preferably from 10 to 14 hours.
In a preferred embodiment, the MIL-47 (V) is obtained by filtration, washing and drying after the hydrothermal reaction-I reaction is completed.
In a preferred embodiment, the process for preparing MILs-101 (V) comprises: vanadium trichloride (VCl) 3 ) And terephthalic acid in solvent II, performing hydrothermal reaction at 110-130deg.C to obtain intermediate product, and thenAnd (3) placing the intermediate product into an N, N-dimethylformamide solution under the protection of inert gas, and performing heating treatment to obtain the MIL-101 (V).
In a preferred embodiment, the solvent II is a water and/or alcohol solvent, preferably water or ethanol.
In a preferred embodiment, the molar ratio of vanadium trichloride to terephthalic acid is 1:0.8-2, preferably 1:1-1.5.
In a preferred embodiment, the ratio of vanadium trichloride to solvent II is 1mmol:1-10mL, preferably 1mmol:4-6mL.
In a preferred embodiment, the dissolution is performed under ultrasound and agitation. Wherein, in the present invention, mixing of vanadium trichloride and terephthalic acid can be promoted by ultrasonic and stirring.
In a preferred embodiment, the reaction temperature of the hydrothermal reaction-II is 115-125 ℃.
In a preferred embodiment, the reaction time of the hydrothermal reaction-II is from 35 to 55 hours, preferably from 40 to 50 hours.
In a preferred embodiment, after the hydrothermal reaction-II reaction is completed, centrifugation and washing are performed to obtain the intermediate product.
In a preferred embodiment, the present invention does not particularly limit the amount 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 60-80 ℃, preferably 65-75 ℃.
In a preferred embodiment, after the heat treatment is completed, the MIL-101 (V) is obtained by centrifugation, washing and drying.
The invention is not particularly limited to ultrasonic treatment, stirring, filtering, washing and drying, and can be carried out according to the conventional 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 conditions of the heat treatment further comprise: the heating rate is 1-5 ℃/min, preferably 1-3 ℃/min; the heat treatment time is 1-5 hours, preferably 2-4 hours.
In a preferred embodiment, the heat treatment is performed in a tube furnace, wherein the metal organic framework material and selenium powder are spaced apart and the selenium powder is located upstream of the tube furnace.
In a second aspect the invention provides a metal-organic framework derived VSe produced by the process of the first aspect of the invention 2 A material.
A third aspect of the invention provides VSe obtainable by a process according to the first aspect of the invention 2 The use of the material in a battery, preferably as electrode material in a lithium ion battery or a sodium ion battery.
The present invention will be described in detail by 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 of ascorbic acid are mixed in 60mL of water, heated and stirred at 45 ℃ for 3 hours, transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, subjected to hydrothermal reaction-I at 180 ℃ for 12 hours, cooled to room temperature, filtered by suction, washed with deionized water and absolute ethyl alcohol for multiple times respectively, and dried in vacuum at 80 ℃ for 12 hours to obtain MIL-47 (V).
Preparation of MIL-101 (V): 10mmol of vanadium trichloride (VCl 3 ) And 10mmol of terephthalic acid (H) 2 BDC) is dissolved in 50mL of water, stirred for 1h, then sonicated for 30min, then transferred into a polytetrafluoroethylene-lined high-pressure reaction kettle, subjected to hydrothermal reaction-II at 120 ℃, cooled to room temperature after 48h of reaction, centrifugally separated at 4000 rpm, and washed with deionized water and absolute ethyl alcohol for multiple times to obtain a green intermediate product; then green is toThe intermediate product is placed in N, N-dimethylformamide solution, heated to 70 ℃ under the protection of nitrogen gas, stirred for 3 hours, centrifugally cleaned at 8000 rpm, and dried in vacuum for 24 hours at 120 ℃ to obtain MIL-101 (V).
Example 1
Placing 0.2g of metal organic framework MIL-47 (V) and 2g of selenium powder in a tubular furnace at intervals, placing the selenium powder at the upstream of the tubular furnace, introducing nitrogen, heating to 500 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3h to obtain VSe derived from the metal organic framework 2 A material.
Example 2
Placing 0.2g of metal organic framework MIL-101 (V) and 2g of selenium powder in a tubular furnace at intervals, wherein the selenium powder is positioned at the upstream of the tubular furnace, introducing nitrogen, heating to 500 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours to obtain VSe derived from the metal organic framework 2 A material.
Comparative example 1
And (3) placing 0.1g of metal organic framework MIL-47 (V) and 2g of selenium powder in a tubular furnace at intervals, wherein the selenium powder is positioned at the upstream of the tubular furnace, introducing nitrogen, heating to 500 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours to obtain the metal organic framework derivative material.
Comparative example 2
And (3) placing 0.2g of metal organic framework MIL-47 (V) and 2g of selenium powder in a tubular furnace at intervals, wherein the selenium powder is positioned at the upstream of the tubular furnace, introducing nitrogen, heating to 400 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours 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, 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 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 acetylacetonate (C 10 H 4 O 5 V) and 2g of selenium powder are placed in a tubular furnace at intervals, the selenium powder is positioned at the upstream of the tubular furnace, nitrogen is introduced, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 3 hours, so that the material is obtained.
Test example 1
VSe derived from the metal organic framework prepared in examples 1-2 2 The material was subjected to XRD characterization, the characterization results are shown in fig. 1 and fig. 2, respectively. XRD characterization was performed on the materials prepared in comparative examples 1 to 5, and the characterization results are shown in FIGS. 3a, 3b, 4a, 4b, and 4c, respectively.
As can be seen from fig. 1 and 2, VSe derived from the metal-organic frameworks prepared in example 1 and example 2 2 Diffraction peaks of material and standard card VSe 2 (JCPDS card number 89-1641) is matched consistently, which shows that the method of the invention can obtain high purity VSe 2 A material.
As can be seen from FIG. 3a, the metal-organic framework derived material prepared in comparative example 1 was modified with V 2 O 3 (JCPDS card number 34-0187) is matched consistently, which shows that excessive selenium powder reacts with MIL-47 (V) of metal organic framework to obtain V 2 O 3 . As can be seen from FIG. 3b, when the heat treatment temperature is relatively low (400 ℃ C.), VSe derived from the prepared metal-organic framework 2 The material contains impurities and has low purity.
As can be seen from FIGS. 4a-4c, the diffraction peaks of the materials obtained when ammonium metavanadate, vanadic anhydride and vanadyl acetylacetonate are used as the vanadium source, respectively, are compared with those of standard card VSe 2 (JCPDS card No. 89-1641) is not matched, namely, under the same condition, the ammonium metavanadate, the vanadium pentoxide and the vanadyl acetylacetonate are selected as vanadium sources and can not be synthesized into VSe 2 。
Test example 2
VSe derived from the metal-organic frameworks prepared in example 1 and example 2 2 The material is subjected to scanning electron microscope characterization, and characterization results are respectively shown in fig. 5 and 6.
As can be seen from FIG. 5, the preparation in example 1VSe derived from the resulting metal-organic frameworks 2 The material is in the shape of a nano rod and has uniform appearance. As can be seen from FIG. 6, the metal-organic framework prepared in example 2 is derived from VSe 2 The material is irregular nano-block particles.
When the metal-organic framework is derived VSe 2 When the nano rod-shaped structure or nano block particles are used as the negative electrode of the lithium ion or sodium ion battery, the transmission distance of the lithium ion or sodium ion can be shortened, and VSe is effectively improved 2 Electrochemical performance of electrode materials in lithium ion or sodium ion batteries.
Test example 3
VSe derived from the metal-organic frameworks prepared in example 1 and example 2 2 The material is subjected to adsorption/desorption characterization, and characterization results are shown in fig. 7 and 8 respectively. Wherein 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 examples 1 and 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. VSe derived from the metal organic framework 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 rich space for lithium ion or sodium ion storage, and can buffer the problems of volume expansion and the like of the electrode material in the circulation process, thereby obtaining the high-performance lithium ion or sodium ion battery.
Test example 4
VSe derived from the metal organic framework prepared in example 1 2 The material is prepared into a lithium ion battery, and the specific preparation method comprises the following steps:
will VSe 2 Materials, carboxylic acidsMethylcellulose and Super P conductive carbon black according to 8:1:1 in a mass ratio of H 2 Mixing in O, and fully grinding to obtain slurry. Subsequently, it was uniformly coated on the copper foil by a coater and dried in a vacuum oven at 110℃for 12 hours. Then cutting the copper foil into pole pieces with a diameter of 14mm, and preparing active substances (VSe 2 Material) is about 1.2mg. The CR2032 button cell is assembled in a glove box with water and oxygen content of less than 0.5ppm by taking metallic lithium as a reference electrode and a counter electrode and Whatman GF/D as a diaphragm. The lithium ion electrolyte comprises 1M lithium hexafluorophosphate dissolved in ethylene carbonate, diethyl carbonate and methyl ethyl carbonate in the mass ratio of 1:1:1.
The constant current cycle performance test (current density of 0.1A/g, voltage of 0.001-3.0V) of the lithium ion battery is carried out by a blue battery tester CT2001A, and the test result is shown in FIG. 9. As can be seen from FIG. 9, the initial coulombic efficiency of the lithium ion battery was 62.7%, the current density was 0.1A/g, and the specific discharge capacity after 50 cycles was 785mAh/g.
The lithium ion battery rate cycle performance test (voltage of 0.001-3.0V) was performed by a blue cell tester CT2001A, and the test results are shown in FIG. 10. As can be seen from fig. 10, the reversible specific capacities were 904.9, 760.0, 687.7, 634.2, 569.7, 476.4mAh/g at current densities of 0.1, 0.2, 0.5, 1, 2, 5A/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 were obtained. Notably, VSe after charging and discharging (after 110 turns) at different current densities 2 The electrode can still keep stable charge-discharge specific capacity, and can be seen to have excellent electrochemical performance as a lithium ion anode material.
Test example 5
VSe derived from the metal-organic framework prepared in example 1 was prepared as in test example 4 2 The material is prepared into a sodium ion battery, which is different from a sodium ion battery which uses metallic sodium as a reference electrode and a counter electrode, wherein sodium perchlorate with the electrolyte component of 1M is dissolved in propylene carbonate and ethylene carbonate with the mass ratio of 1:1.
The constant current cycle performance test and the rate cycle performance test were performed on the sodium ion battery 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 turns, it can provide a reversible specific capacity of 288.8 mAh/g. As can be seen from fig. 12, the reversible specific capacities were 389.5, 294.7, 207.8, 145.7, 105.1 and 80.6mAh/g at current densities of 0.1, 0.2, 0.5, 1, 2 and 5A/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 were obtained. Description of the results VSe 2 The material has excellent sodium ion storage performance.
Test example 6
The metal-organic framework derived VSe prepared in example 2 was prepared as in test example 4 2 The materials were prepared into lithium ion batteries, and constant current cycle performance test and rate cycle performance test were performed on the lithium ion batteries according to the method in test example 4, and the test results are shown in fig. 13 and 14.
As is clear from FIG. 13, the initial coulombic efficiency was 62.5%, and after 50 cycles, the specific discharge capacity was 755mAh/g at a current density of 0.1A/g. As can be seen from fig. 14, the reversible specific capacities were 776.6, 688.3, 638.3, 590, 531.4, 438.6mAh/g at current densities of 0.1, 0.2, 0.5, 1, 2, 5A/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 768.3, 762.4, 686.5, 643 and 569.7mAh/g were obtained. Notably, VSe after charging and discharging (after 110 turns) at different current densities 2 The electrode can still keep stable charge-discharge specific capacity, and can be seen to have better electrochemical performance when being used as a lithium ion anode material.
Test example 7
The same as in test example 5, except that VSe derived from the metal-organic framework prepared in example 2 2 The material was prepared into a sodium ion battery, and the constant current cycle performance test and the multiplying power cycle performance test were performed on the sodium ion battery 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, it provides a reversible specific capacity of 224.1mAh/g after 50 turns. As can be seen from fig. 16, the reversible specific capacities were 264.2, 229.9, 175.6, 137.7, 107.6, and 81.9mAh/g at current densities of 0.1, 0.2, 0.5, 1, 2, and 5A/g, respectively. Further, when the current density was restored to 0.1, 0.2, 0.5, 1 and 2A/g, reversible specific capacities of 231.3, 201.9, 151.8, 121.1 and 96mAh/g were obtained.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. VSe derived from metal-organic framework 2 A method of preparing a material, the method comprising: performing heat treatment on the metal organic framework material containing the V element and the selenium powder in an inert atmosphere to obtain VSe 2 A material;
wherein the metal organic framework material comprises MIL-47 (V) and/or MIL-101 (V);
wherein, the mass ratio of the metal organic framework material to the selenium powder is 1:2-15, wherein the heat treatment temperature is 450-550 ℃.
2. The preparation method of claim 1, wherein the preparation method of MILs-47 (V) comprises: mixing vanadium pentoxide, terephthalic acid and ascorbic acid in a solvent I, and performing hydrothermal reaction-I at 170-190 ℃ to obtain MIL-47 (V).
3. The preparation method according to claim 2, wherein the molar ratio of vanadium pentoxide, terephthalic acid and ascorbic acid is 1:7-10:0.5-3.5;
and/or the dosage ratio of vanadium pentoxide to the solvent I is 1mmol:50-110 and mL;
and/or, the reaction temperature of the hydrothermal reaction-I is 175-185 ℃;
and/or the reaction time of the hydrothermal reaction-I is 8-16h.
4. The preparation method according to claim 3, wherein the molar ratio of vanadium pentoxide, terephthalic acid and ascorbic acid is 1:8-9:1.5-2.5;
and/or the dosage ratio of vanadium pentoxide to the solvent I is 1mmol:70-90 mL;
and/or the reaction time of the hydrothermal reaction-I is 10-14h.
5. The preparation method of claim 1, wherein the preparation method of MILs-101 (V) comprises: dissolving vanadium trichloride and terephthalic acid in a solvent II, performing 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 to obtain MIL-101 (V).
6. The process according to claim 5, wherein the molar ratio of vanadium trichloride to terephthalic acid is 1:0.8-2;
and/or the dosage ratio of vanadium trichloride to solvent II is 1mmol:1-10 mL;
and/or, the reaction temperature of the hydrothermal reaction-II is 115-125 ℃;
and/or the hydrothermal reaction-II has a reaction time of 35-55 h.
7. The process according to claim 6, wherein the molar ratio of vanadium trichloride to terephthalic acid is 1:1 to 1.5;
and/or the dosage ratio of vanadium trichloride to solvent II is 1mmol:4-6 mL;
and/or the hydrothermal reaction-II has a reaction time of 40-50h.
8. The preparation method according to claim 5, wherein the heating is performed under stirring at a heating temperature of 60 to 80 ℃.
9. The production method according to claim 8, wherein the heating is performed with stirring at a heating temperature of 65 to 75 ℃.
10. The preparation method according to any one of claims 1 to 9, wherein the mass ratio of the metal-organic framework material to the selenium powder is 1:8-12;
and/or, the conditions of the heat treatment further include: the temperature rising rate is 1-5 ℃/min, and the heat treatment time is 1-5 h.
11. The preparation method of claim 10, wherein the mass ratio of the metal organic framework material to the selenium powder is 1:8-12;
and/or, the conditions of the heat treatment further include: the temperature rising rate is 1-3 ℃/min, and the heat treatment time is 2-4h.
12. VSe derived from a metal-organic framework prepared by a process according to any one of claims 1 to 11 2 A material.
13. VSe as claimed in claim 12 2 The application of the material in the battery.
14. The use according to claim 13, wherein the use is as electrode material in a lithium ion battery or a sodium ion battery.
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