CN109638257B - Composite vanadium pentoxide material and preparation method and application thereof - Google Patents
Composite vanadium pentoxide material and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
Abstract
The invention provides a composite vanadium pentoxide material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) dispersing a carbon source in deionized water to form a dispersion liquid; (2) adding a vanadium source and a doping element source into the dispersion liquid obtained in the step (1), and carrying out hydrothermal reaction to obtain the composite vanadium pentoxide material; according to the preparation method provided by the invention, the carbon source preparation dispersion liquid and the vanadium source and the doping element source form composite doping, the conductivity and the structural stability of the vanadium pentoxide material are improved by two technical means, the preparation method is simple in process, mild in reaction condition, suitable for industrial production, free of pollution and low in production cost, and when the prepared composite vanadium pentoxide material is applied to a lithium-magnesium hybrid battery, the first charge-discharge reversible specific capacity is 200-250 mAh/g, and the preparation method has a high application value.
Description
Technical Field
The invention belongs to the field of electrochemistry, and relates to a composite vanadium pentoxide material, a preparation method and application thereof.
Background
Magnesium secondary batteries are considered to be a novel type of secondary battery with great potential. The core of the magnesium secondary battery is a Mg negative electrode, an organic electrolyte solution and a positive electrode material with good magnesium ion extraction performance. The research on the magnesium ion deintercalation material starts in the seventies of the last century, but the industrial production is not formed so far, and the development of the magnesium secondary battery is limited by the following two main technical difficulties: on one hand, compared with lithium ions, magnesium ions have small radius, large charge density and more serious solvation, so that the magnesium ions are more difficult to be embedded into a general cathode material than the lithium ions, and the magnesium ions also move slowly in the cathode material; on the other hand, magnesium forms a layer of compact passivation film in most electrolyte, so that the migration of magnesium ions is prevented, the magnesium ions cannot be reversibly deposited and dissolved out, and the electrochemical performance of the magnesium ions is influenced. Because of the problems of both lithium and magnesium batteries, a lithium-magnesium hybrid battery, a battery system with a positive electrode material, a lithium-magnesium composite electrolyte and a magnesium negative electrode, has been designed, and the most important of them is the selection of the positive electrode material with high performance and the related preparation problems.
V of biorthogonal system2O5From one layer to one layer of VO5Square pyramid composition, VO5Occupies the edges and corners of each layer. The distance from the V-O bond at the top is longer than the distances in all the other four directions, and corresponds to the distance of one double bond. V2O5The layered structure of (a) illustrates the two-dimensional characteristics of such a material; however, V2O5Can also be regarded as a twisted VO6Octahedron. The length of the six V-O bonds is very large, which enables foreign atoms to be inserted into its perovskite-like voids. The open layered structure provides a good space channel for the de-intercalation of lithium ions, and 1mol of vanadium pentoxide with the layered structure can be inserted into 2mol of Li+The theoretical capacity can reach 294mAh/g, and vanadium pentoxide is rich in resource and easy to prepare, and is a magnesium-lithium hybrid battery positive electrode material with great potential. However, vanadium pentoxide, as a positive electrode material, also has low electronic conductivity (10)-2～10-3S/cm), slow ion diffusivity (10)-12～10-13cm2And/s), which results in poor cycle performance and rate performance of the vanadium pentoxide cathode material in the charging and discharging processes.
CN108483496A discloses a preparation method of a vanadium dioxide nano flaky material, which comprises the following steps: (1) dropwise adding an acidic substance into a vanadium source aqueous solution, and raising the temperature to stir the solution after the dropwise adding of the acidic substance is finished; (2) after the stirring is finished, performing aging treatment on the obtained product to obtain a crude product of the vanadium dioxide nano flaky material; (3) and (3) carrying out heat treatment on the crude product of the vanadium dioxide nano flaky material obtained in the step (2) to obtain the vanadium dioxide nano flaky material. The material has uniform size and uniform particle distribution, and when the material is used as the anode material of the lithium-magnesium hybrid battery, the reversible specific capacity of charge and discharge for the first time is high. However, the material system prepared by the method is single, and the conductivity and the structural stability of the material system need to be further enhanced.
CN108155359A discloses a vanadium pentoxide/graphene/hollow carbon sphere nanocomposite positive electrode plate and a preparation method of a lithium ion button cell thereof. The hollow carbon spheres are introduced into the vanadium pentoxide/graphene composite material, the excellent conductivity of the vanadium pentoxide/graphene and the hollow carbon spheres with rich pore structures are combined to generate a synergistic effect, on one hand, polymerization reaction can occur between the graphene oxide and the hollow carbon spheres, so that the hollow carbon spheres and the graphene have a bonding effect, and a uniform graphene-hollow carbon sphere composite structure can be formed, on the other hand, the existence of the hollow carbon spheres also prevents graphene sheet layers from being stacked again, which is beneficial to obtaining the graphene with fewer layers, the electrical property of the vanadium pentoxide/graphene anode material is greatly improved, and the specific capacity of 100 times of charge and discharge reaches 683 mAh/g. However, the method still has the problem of single system.
CN103855373A discloses a preparation method of a vanadium pentoxide/graphene composite material, which comprises the following steps: adding graphite oxide into acetone, and carrying out ultrasonic treatment for 30-180 min to form a suspension of 0.006-0.053 mg/mL; adding triisopropoxyl vanadium oxide and distilled water into the suspension, sealing, and aging at room temperature for 2-5 days to obtain wet gel; wherein the volume ratio of acetone, triisopropoxyl vanadium oxide and distilled water is 5-15: 1: 2-5; taking out the wet gel, washing the wet gel for several times by adopting anhydrous acetone and cyclohexane in sequence, and drying to obtain dry gel; and placing the obtained xerogel in an inert gas protective atmosphere, and reacting at the high temperature of 500-700 ℃ for 1-10 h to obtain the vanadium pentoxide/graphene composite material. The method has the disadvantages of complicated preparation process and high limitation.
In order to solve the problems of the materials, a composite vanadium pentoxide material needs to be designed as a positive electrode material of the lithium-magnesium ion battery, so that the material has excellent electrochemical performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite vanadium pentoxide material, a preparation method and application thereof, so that the vanadium pentoxide material achieves the effects of uniform appearance and uniform distribution, and has the characteristic of high charge-discharge reversible specific capacity when being used as a positive electrode material of a lithium-magnesium hybrid battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a composite vanadium pentoxide material, which is characterized by comprising the following steps:
(1) dispersing a carbon source in water to form a dispersion;
(2) and (2) adding a vanadium source and a doping element source into the dispersion liquid obtained in the step (1), and carrying out hydrothermal reaction to obtain the composite vanadium pentoxide material.
According to the preparation method provided by the invention, the carbon source is used for preparing the dispersion liquid, and the vanadium source and the doping element source form composite doping, so that the conductivity and the structural stability of the vanadium pentoxide material are improved by two technical means; and the preparation method has simple process, mild reaction conditions, no pollution and low production cost, and is suitable for industrial production.
The water according to the present invention may be deionized water, ultrapure water, or the like.
Preferably, the carbon source in step (1) is an inorganic carbon source.
Preferably, the inorganic carbon source includes any one of graphite, activated carbon, graphene, nitrogen-doped graphene, graphene oxide, carbon nanotubes, or porous carbon.
Preferably, the inorganic carbon source is graphene oxide.
Preferably, the concentration of the carbon source in the dispersion liquid in the step (1) is 0.05 to 1mol/L, for example, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.8mol/L, or 1mol/L, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the concentration of the carbon source in the dispersion liquid in the step (1) is 0.1-0.5 mol/L.
Preferably, the dispersion in step (1) is carried out under ultrasonic conditions.
Preferably, the time of the ultrasonic treatment is 10-120 min, for example, 10min, 20min, 50min, 80min, 100min or 120min, and preferably 30-300 min.
Preferably, the vanadium source in step (2) comprises any one of ammonium metavanadate, sodium metavanadate or vanadium pentoxide or a combination of at least two of the above.
Preferably, the doping element in the doping element source in the step (2) includes any one or a combination of at least two of nitrogen, fluorine, sulfur, phosphorus or chlorine.
Preferably, the phosphorus element is provided by any one of elemental phosphorus, an organic phosphorus compound, or an inorganic phosphorus compound, or a combination of at least two thereof. Organic phosphorus compounds are preferred.
Preferably, the organophosphorus compound comprises any one or a combination of at least two of phosphonitrile trichloride chloride, adenosine triphosphate, adenosine diphosphate, phosphoenone acetonic acid, phosphate ester, tetrakis hydroxymethyl phosphonium chloride, dimethyl vinylphosphate, hexachlorocyclotriphosphazene, polydichlorophosphazene, polyalkoxyphosphazene, polyaryloxy phosphazene or polyfluorooxyphosphazene.
Preferably, the inorganic phosphorus compound comprises any one of sodium phosphate, potassium phosphate, or phosphoric acid, or a combination of at least two thereof.
Preferably, the elemental sulfur is provided by any one or a combination of at least two of sodium sulfide, sodium thiosulfate, thiourea, thiol, thiophenol, thioether, disulfide, polysulfide, cyclic sulfide, diallyl thiosulfonate, diallyl trisulfide or diallyl disulfide.
Preferably, the nitrogen element is provided by ammonium nitrate.
Preferably, the fluorine element is provided by ammonium fluoride.
Preferably, the chlorine element is provided by ammonium chloride and/or hydrochloric acid.
Preferably, the concentration of vanadate ions formed in the dispersion liquid by the vanadium source in the step (2) is 1-10 mol/L, and may be 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, mol/L, 8mol/L, 9mol/L or 10mol/L, for example.
Preferably, the concentration of the doping element formed in the dispersion liquid by the doping element source in the step (2) is 0.05-0.2 mol/L, and may be, for example, 0.05mol/L, 0.08mol/L, 0.1mol/L, 0.13mol/L, 0.16mol/L, 0.19mol/L, 0.2mol/L, or the like.
Preferably, the vanadium source and the doping element source in step (2) are added to the dispersion under stirring.
Preferably, the stirring speed is 500-1500 r/min, such as 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, 1200r/min, 1400r/min or 1500r/min, preferably 800-1000 r/min.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 160 to 220 ℃, for example, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220, etc., preferably 170 to 190 ℃;
preferably, the hydrothermal reaction time in step (2) is 2-48 h, for example, 2h, 5h, 10h, 15h, 25h, 30h, 38h, 40h or 48h, etc.
Preferably, after the hydrothermal reaction in the step (2) is finished, precipitating, centrifuging, washing and drying to obtain the composite vanadium pentoxide material.
Preferably, the preparation method comprises the following steps:
(1) ultrasonically dispersing a carbon source in water within 10-120 min to form a dispersion liquid with the concentration of 0.05-1 mol/L;
(2) adding a vanadium source and a doping element source into the dispersion liquid obtained in the step (1) at a stirring speed of 500-1500 r/min, stirring until the vanadium source and the doping element source are completely dissolved, enabling the concentration of vanadate ions formed in the dispersion liquid to be 1-10 mol/L and the concentration of the doping element to be 0.05-0.2 mol/L, carrying out hydrothermal reaction at the temperature of 160-220 ℃ for 2-48 h, and carrying out precipitation, centrifugation, washing and drying to obtain the composite vanadium pentoxide material.
In a second aspect, the invention provides the composite vanadium pentoxide material prepared by the preparation method of the first aspect, wherein a high-conductivity carbon material and the vanadium pentoxide with the oxygen site doped and modified layered structure form a good composite, which makes it possible for the material to have good electrochemical properties.
In a third aspect, the invention provides a use of the composite vanadium pentoxide material according to the first aspect in preparation of a positive electrode material of a lithium-magnesium ion battery.
According to the invention, the composite vanadium pentoxide material with uniform size is obtained through a specific process, so that the double purposes of nanocrystallization and improvement of the conductivity of the material are achieved, the problem of lithium and magnesium ion deintercalation at the positive electrode is further solved, and meanwhile, the composite vanadium pentoxide material has excellent electrochemical performance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the composite vanadium pentoxide material provided by the invention is simple in process, mild in reaction conditions, suitable for industrial production, pollution-free and low in production cost, improves the conductivity and structural stability of the vanadium pentoxide material by two composite doping technical means, and can be used as a magnesium ion battery anode material.
(2) When the composite vanadium pentoxide material provided by the invention is applied to a lithium-magnesium hybrid battery, the reversible specific capacity of charge and discharge for the first time is 200-250 mAh/g, and compared with the material prepared by other related methods at present, the composite vanadium pentoxide material has better performance and higher application value.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a composite vanadium pentoxide material, which comprises the following steps:
(1) taking graphene oxide powder and deionized water, and carrying out ultrasonic dispersion to prepare a dispersion liquid, wherein the concentration of the dispersion liquid is 0.1mol/L, and the ultrasonic time is 30 min.
(2) And (2) dissolving vanadium pentoxide and thiourea serving as a vanadium source and a sulfur source in the solution, wherein the concentration of vanadium-containing acid radical ions in the solution is 1mol/L, the concentration of sulfur in the solution is 0.05mol/L, and continuously stirring until the vanadium-containing acid radical ions are completely dissolved, wherein the stirring speed is 500 r/min.
(3) And carrying out hydrothermal reaction on the uniform solution at 180 ℃ for 12h to obtain a precipitate, and carrying out centrifugal washing and drying to obtain the composite vanadium pentoxide material.
The obtained composite vanadium pentoxide material is used as a lithium-magnesium ion battery anode material for electrochemical performance test, and the mass ratio of the pole piece is as follows: acetylene black: PVDF is 8:1:1, and the electrolyte is (0.2mol/L [ Mg)2Cl2(DME)4][AlCl4]2And 1.0mol/L LiTFSI). And preparing the CR2025 button cell by taking a magnesium sheet as a reference electrode. Under the voltage window of 1-3.0V and the multiplying power of 0.1C, the first cyclic discharge specific capacity and the first charge specific capacity are 265mAh/g and 250mAh/g respectively.
Example 2
The embodiment provides a preparation method of a composite vanadium pentoxide material, which comprises the following steps:
(1) taking graphite powder and deionized water, and carrying out ultrasonic dispersion to prepare a dispersion liquid, wherein the concentration of the solution is 0.1mol/L, and the ultrasonic time is 30 min.
(2) And dissolving vanadium pentoxide and thiourea serving as vanadium source sulfur sources in the solution, wherein the concentration of vanadium-containing acid radical ions in the solution is 1mol/L, the sulfur concentration is 0.05mol/L, and continuously stirring until the vanadium-containing acid radical ions are completely dissolved, wherein the stirring speed is 500 r/min.
(3) And carrying out hydrothermal reaction on the uniform solution at 180 ℃ for 12h to obtain a precipitate, and carrying out centrifugal washing and drying to obtain the composite vanadium pentoxide material.
The obtained composite vanadium pentoxide material is used as a lithium-magnesium ion battery anode material for electrochemical performance test, and the mass ratio of the pole piece is as follows: acetylene black: PVDF is 8:1:1, and the electrolyte is (0.2mol/L [ Mg)2Cl2(DME)4][AlCl4]2And 1.0mol/L LiTFSI). And preparing the CR2025 button cell by taking a magnesium sheet as a reference electrode. Under the voltage window of 1-3.0V and the multiplying power of 0.1C, the first cyclic discharge specific capacity and the first charge specific capacity are 220mAh/g and 200mAh/g respectively.
Example 3
The embodiment provides a preparation method of a composite vanadium pentoxide material, which comprises the following steps:
(1) taking graphene oxide powder and deionized water, and carrying out ultrasonic dispersion to prepare a dispersion liquid, wherein the concentration of the dispersion liquid is 0.1mol/L, and the ultrasonic time is 30 min.
(2) And dissolving vanadium pentoxide and sodium phosphate as vanadium source phosphorus sources in the solution, wherein the concentration of vanadium-containing acid radical ions in the solution is 1mol/L, the phosphorus concentration is 0.05mol/L, and continuously stirring until the vanadium-containing acid radical ions are completely dissolved, wherein the stirring speed is 500 r/min.
(3) And carrying out hydrothermal reaction on the uniform solution at 180 ℃ for 12h to obtain a precipitate, and carrying out centrifugal washing and drying to obtain the composite vanadium pentoxide material.
The obtained composite vanadium pentoxide material is used as a lithium-magnesium ion battery anode material for electrochemical performance test, and the mass ratio of the pole piece is as follows: acetylene black: PVDF is 8:1:1, and the electrolyte is (0.2mol/L [ Mg)2Cl2(DME)4][AlCl4]2And 1.0mol/L LiTFSI). And preparing the CR2025 button cell by taking a magnesium sheet as a reference electrode. Under the voltage window of 1-3.0V and the multiplying power of 0.1C, the first cyclic discharge specific capacity and the first charge specific capacity are 220mAh/g and 210mAh/g respectively.
Example 4
The embodiment provides a preparation method of a composite vanadium pentoxide material, which comprises the following steps:
(1) taking graphene oxide powder and water, and carrying out ultrasonic dispersion to prepare a dispersion liquid, wherein the concentration of the solution is 0.05mol/L, and the ultrasonic time is 120 min.
(2) And dissolving vanadium pentoxide and thiourea serving as vanadium source sulfur sources in the solution, wherein the concentration of vanadium-containing acid radical ions in the solution is 1mol/L, the sulfur concentration is 0.05mol/L, and continuously stirring until the vanadium-containing acid radical ions are completely dissolved, wherein the stirring speed is 500 r/min.
(3) And carrying out hydrothermal reaction on the uniform solution at 220 ℃ for 2h to obtain a precipitate, and carrying out centrifugal washing and drying to obtain the composite vanadium pentoxide material.
The obtained composite vanadium pentoxide material is used as a lithium-magnesium ion battery anode material for electrochemical performance test, and the mass ratio of the pole piece is as follows: acetylene black: PVDF is 8:1:1, and the electrolyte is (0.2mol/L [ Mg)2Cl2(DME)4][AlCl4]2And 1.0mol/L LiTFSI). And preparing the CR2025 button cell by taking a magnesium sheet as a reference electrode. Under the voltage window of 1-3.0V and the multiplying power of 0.1C, the first cyclic discharge specific capacity and the first charge specific capacity are respectively 250mAh/g and 220 mAh/g.
Example 5
The embodiment provides a preparation method of a composite vanadium pentoxide material, which comprises the following steps:
(1) taking activated carbon and deionized water, and carrying out ultrasonic dispersion to prepare a dispersion solution, wherein the concentration of the solution is 1mol/L, and the ultrasonic time is 10 min.
(2) And (2) dissolving sodium metavanadate and thioether serving as vanadium source sulfur sources in the solution, wherein the concentration of vanadium-containing acid radical ions in the solution is 10mol/L, the sulfur concentration is 0.05mol/L, and continuously stirring until the vanadium-containing acid radical ions are completely dissolved, wherein the stirring speed is 1500 r/min.
(3) And carrying out hydrothermal reaction on the uniform solution at 160 ℃ for 48h to obtain a precipitate, and carrying out centrifugal washing and drying to obtain the composite vanadium pentoxide material.
The obtained composite vanadium pentoxide material is used as a lithium-magnesium ion battery anode material for electrochemical performance test, and the mass ratio of the pole piece is as follows: acetylene black: PVDF is 8:1:1, and the electrolyte is (0.2mol/L [ Mg)2Cl2(DME)4][AlCl4]2And 1.0mol/L LiTFSI). And preparing the CR2025 button cell by taking a magnesium sheet as a reference electrode. Under the voltage window of 1-3.0V and the multiplying power of 0.1C, the first cyclic discharge specific capacity and the first charge specific capacity are 240mAh/g and 230mAh/g respectively.
Example 6
In this example, the conditions were the same as those in example 1 except that the vanadium pentoxide in step (1) was replaced with ammonium metavanadate.
Example 7
In this example, the conditions were the same as in example 1 except that the stirring time in step (2) was changed to 1000 r/min.
Example 8
In this example, the conditions were the same as in example 1 except that the ultrasonic time in step (1) was changed to 60 min.
Comparative example 1
In this comparative example, the conditions were the same as in example 1 except that the water in step (1) was replaced with ethanol.
The composite vanadium pentoxide material with uniform size cannot be obtained by the preparation method of the comparative example.
Comparative example 2
In this comparative example, the conditions were the same as in example 1 except that the sonication in step (1) was replaced with simple stirring.
The composite vanadium pentoxide material with uniform size cannot be obtained by the preparation method of the comparative example.
Comparative example 3
In this comparative example, no other doping element was added in step (2), and the other conditions were the same as in example 1.
The electrochemical performance of the material prepared by the preparation method of the comparative example is relatively poor, and the first discharge specific capacity is only 190 mAh/g.
It can be seen from examples 1 to 8 and comparative examples 1 to 3 that the preparation method of the present invention is obtained by comprehensively preparing a plurality of process conditions such as solvent selection, reactant selection, heat treatment, etc., and when any one step is absent or the process is changed, the composite vanadium pentoxide material cannot be obtained because the size is not uniform and the structure is not stable.
The composite vanadium pentoxide series material prepared in the embodiments 1-8 of the invention is used for the anode material of the magnesium ion battery, and the anode material has excellent electrochemical performance, and the reversible specific capacity of charge and discharge for the first time can reach 200-250 mAh/g.
The applicant states that the composite vanadium pentoxide material, the preparation method and the application thereof are illustrated by the above examples, but the invention is not limited to the above detailed method, i.e. the invention is not meant to be implemented by relying on the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (17)
1. The application of the composite vanadium pentoxide material in the preparation of the positive electrode material of the lithium-magnesium ion battery is characterized in that the preparation method of the composite vanadium pentoxide material comprises the following steps:
(1) dispersing a carbon source in water to form a dispersion;
(2) adding a vanadium source and a doping element source into the dispersion liquid obtained in the step (1), and carrying out hydrothermal reaction to obtain the composite vanadium pentoxide material;
the doping element in the doping element source in the step (2) comprises sulfur element and/or phosphorus element;
the phosphorus element is provided by an inorganic phosphorus compound;
the sulfur element is provided by any one or combination of at least two of sodium sulfide, sodium thiosulfate, thiourea, mercaptan, thiophenol, thioether, disulfide, polysulfide, cyclic sulfide, diallyl thiosulfonate, diallyl trisulfide or diallyl disulfide;
the dispersion in the step (1) is carried out under the ultrasonic condition, and the ultrasonic time is 10-120 min;
in the step (1), the carbon source is any one or a combination of at least two of graphene oxide powder, graphite powder or activated carbon;
and (3) the vanadium source in the step (2) is vanadium pentoxide.
2. The use according to claim 1, wherein the concentration of the carbon source in the dispersion liquid in the step (1) is 0.05 to 1 mol/L.
3. The use according to claim 2, wherein the carbon source concentration in the dispersion liquid of step (1) is 0.1-0.5 mol/L.
4. The use according to claim 1, wherein the ultrasound is carried out for a period of 30 to 300 min.
5. Use according to claim 1, characterized in that the phosphorus element is provided by an organophosphorus compound.
6. Use according to claim 5, wherein the organophosphorus compound comprises any one of or a combination of at least two of phosphonitrilic triphosphoryl chloride, adenosine triphosphate, adenosine diphosphate, phosphoenone pyruvate, phosphate esters, tetrakis hydroxymethyl phosphonium chloride, dimethyl vinylphosphate, hexachlorocyclotriphosphazene, polydichlorophosphazene, polyalkoxyphosphazene, polyaryloxy phosphazene or polyfluorooxyphosphazene.
7. Use according to claim 1, wherein the inorganic phosphorus compound comprises any one of sodium phosphate, potassium phosphate or phosphoric acid or a combination of at least two thereof.
8. The use according to claim 1, wherein the vanadium source in step (2) forms vanadate ions at a concentration of 1 to 10mol/L in the dispersion.
9. The use according to claim 1, wherein the doping element source in step (2) is formed in the dispersion at a concentration of 0.05 to 0.2 mol/L.
10. Use according to claim 1, characterized in that in step (2) the source of vanadium and the source of doping element are added to the dispersion under stirring.
11. Use according to claim 10, wherein the stirring is at a rate of 500 to 1500 r/min.
12. Use according to claim 11, wherein the stirring is at a rate of 800 to 1000 r/min.
13. The use according to claim 1, wherein the temperature of the hydrothermal reaction in step (2) is 160-220 ℃.
14. The use according to claim 13, wherein the temperature of the hydrothermal reaction in step (2) is 170-190 ℃.
15. The use according to claim 1, wherein the hydrothermal reaction time in step (2) is 2-48 h.
16. The use of claim 1, wherein after the hydrothermal reaction in step (2) is finished, the method further comprises the steps of precipitating, centrifuging, washing and drying to obtain the composite vanadium pentoxide material.
17. Use according to claim 1, characterized in that the preparation process comprises the following steps:
(1) ultrasonically dispersing a carbon source in water within 10-120 min to form a dispersion liquid with the concentration of 0.05-1 mol/L;
(2) adding a vanadium source and a doping element source into the dispersion liquid obtained in the step (1) at a stirring speed of 500-1500 r/min, stirring until the vanadium source and the doping element source are completely dissolved, enabling the concentration of vanadate ions formed in the dispersion liquid to be 1-10 mol/L and the concentration of the doping element to be 0.05-0.2 mol/L, carrying out hydrothermal reaction at the temperature of 160-220 ℃ for 2-48 h, and carrying out precipitation, centrifugation, washing and drying to obtain the composite vanadium pentoxide material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN110078121A (en) * | 2019-05-21 | 2019-08-02 | 上海交通大学 | A kind of preparation method and application of Magnesium ion battery vanadic anhydride positive electrode |
| CN113912877A (en) * | 2020-07-08 | 2022-01-11 | Tcl科技集团股份有限公司 | Composite film, quantum dot light-emitting diode and preparation method thereof |
| CN111900398A (en) * | 2020-07-13 | 2020-11-06 | 西安交通大学 | Magnesium-doped vanadium pentoxide nanoribbon positive electrode material, preparation method thereof and water-based zinc ion battery |
| CN113481656B (en) * | 2021-06-30 | 2022-09-20 | 攀钢集团研究院有限公司 | Preparation method of high-purity vanadium pentoxide nanofiber non-woven fabric |
| CN114275812B (en) * | 2021-12-23 | 2022-08-16 | 西安交通大学 | graphene/Li x V 2 O 5 Composite electrode material, preparation method and application thereof |
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