CN114031063B - Sodium vanadium fluorophosphate nanocomposite and preparation method thereof - Google Patents
Sodium vanadium fluorophosphate nanocomposite and preparation method thereof Download PDFInfo
- Publication number
- CN114031063B CN114031063B CN202111301879.XA CN202111301879A CN114031063B CN 114031063 B CN114031063 B CN 114031063B CN 202111301879 A CN202111301879 A CN 202111301879A CN 114031063 B CN114031063 B CN 114031063B
- Authority
- CN
- China
- Prior art keywords
- sodium
- vanadium
- fluorophosphate
- vanadium fluorophosphate
- sodium vanadium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/58—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
- H01M4/582—Halogenides
-
- 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
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 relates to a sodium vanadium fluorophosphate nanocomposite and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Dissolving vanadium pentoxide and oxalic acid in deionized water to obtain a tetravalent vanadium solution; (2) Mixing the tetravalent vanadium solution obtained in the step (1) with ammonium dihydrogen phosphate, sodium fluoride and ethylene glycol to obtain a trivalent vanadium solution; (3) Mixing the carbon nano tube with the trivalent vanadium solution obtained in the step (2), stirring and uniformly dispersing to obtain a mixed solution; (4) And (4) carrying out solvent thermal reaction on the mixed solution obtained in the step (3), filtering, washing and drying after the reaction is finished. The nano-vanadium fluorophosphate carbon nano-tube composite material has a three-dimensional continuous network structure, wherein the sodium vanadium fluorophosphate has a nano-sheet shape, the surface of the nano-sheet is coated with a carbon layer, the sodium vanadium fluorophosphate nano-sheets are stacked into micro-columns layer by layer and are dispersed in a three-dimensional conductive network structure formed by the carbon nano-tubes, and the nano-vanadium fluorophosphate carbon nano-tube composite material has the discharge specific capacity close to the theoretical specific capacity, excellent cycle performance and rate capability and excellent market application prospect.
Description
Technical Field
The invention relates to the field of sodium ion batteries, in particular to a sodium vanadium fluorophosphate nanocomposite and a preparation method thereof.
Background
Lithium ion batteries have been widely used in portable electronic devices and electric vehicles because of their advantages of high energy density, high power density, long cycle life, and the like. However, because of the relative shortage of lithium resources, uneven distribution and difficult extraction, the application of lithium ion batteries to the large-scale energy storage field still has cost limitation.
Sodium and lithium have similar electrochemical de-intercalation mechanisms, and sodium is abundant in earth crust and low in price, so that the sodium-ion battery can be used as an ideal system for large-scale energy storage. However, sodium has a greater atomic mass and higher standard electrode potential than lithium, resulting in a lower energy density of sodium-ion batteries; in addition, the radius of the sodium ions is larger than that of the lithium ions, so that the diffusion kinetics of the sodium ions are slow, and the volume strain of a host material is easily caused, so that the cycle life of the sodium ion battery is short. Therefore, the search for an electrode material with a suitable sodium ion deintercalation structure is crucial to the development and application of sodium ion batteries.
The polyanion phosphate anode material has high structural stability due to the two-dimensional or three-dimensional sodium ion diffusion channel, so that the polyanion phosphate anode material is widely researched. Polyanion type positive electrode material vanadium sodium fluorophosphate (Na) with sodium fast ion conductor (NASICON) structure 3 V 2 (PO 4 ) 2 F 3 ) The material is considered to be a sodium-ion battery positive electrode material with promising application prospect due to the high voltage platform (the average voltage platform is 3.95V) and the high theoretical specific capacity (128 Ah/kg). But due to Na 3 V 2 (PO 4 ) 2 F 3 The electron conductivity of (2) is poor, so that the actual capacity of the material is difficult to reach a theoretical value, and the rate capability of the material is poor.
Against Na 3 V 2 (PO 4 ) 2 F 3 The conventional modification method is to coat the surface with carbon or to compound the carbon material. For example, patent application CN109755489A discloses a sodium vanadium fluorophosphate/carbon compositeThe preparation method comprises the following steps: 1) Weighing sodium salt, a vanadium source, phosphate, fluoride and a reducing agent according to the molar ratio of sodium, vanadium, phosphate radical, fluorine and reducing agent of 3; 2) Adding the sodium salt, the vanadium source, the phosphate, the villaumite and the reducing agent in the step 1) into a hydrothermal kettle at the temperature of 100-300 ℃, adding a solvent, adding an additive, and reacting for 3-72 hours; 3) Filtering the mixture obtained in step 2), washing with deionized water and ethanol for 2-5 times, and maintaining at 100-150 deg.C for 1-20 hr to obtain Na 3 V 2 (PO 4 ) 2 F 3 (ii) a 4) Na obtained in the step 3) 3 V 2 (PO 4 ) 2 F 3 Mixing with carbon material, ball milling for 0.1-24 hr at 400-2000rpm to obtain Na 3 V 2 (PO 4 ) 2 F 3 a/C complex. However, na produced by this method 3 V 2 (PO 4 ) 2 F 3 Large particle size, difficult uniform dispersion of carbon material when the carbon material is compounded by ball milling, and high compatibility with Na 3 V 2 (PO 4 ) 2 F 3 The improvement in conductivity is limited.
Patent application CN109841800A discloses a sodium vanadium fluorophosphate and carbon composite, and its preparation and application, which is prepared by the following steps: 1) Weighing sodium salt, vanadium source, phosphate, villiaumite, reducing agent, carbon source and additive according to the molar ratio of sodium, vanadium, phosphate radical, fluorine, reducing agent, carbon and additive of 3; 2) Adding the mixture obtained in the step 1) into a hydrothermal kettle at the temperature of 100-300 ℃, adding a solvent, and reacting for 3-72h; 3) Filtering the mixed solution obtained in step 2), respectively washing with deionized water and ethanol for 2-5 times, and maintaining at 100-150 deg.C for 1-20 hr to obtain Na 3 V 2 (PO 4 ) 2 F 3 A carbon composite. By introducing a carbon source in Na during the solvothermal reaction 3 V 2 (PO 4 ) 2 F 3 A carbon layer is formed on the surface to increase Na 3 V 2 (PO 4 ) 2 F 3 The conductivity of the particles, but the surface-coated carbon is generally amorphous carbon, for Na 3 V 2 (PO 4 ) 2 F 3 The degree of improvement in conductivity is limited and the conductivity between particles is not effectively increased.
Disclosure of Invention
The invention aims to overcome the defects of low conductivity of the vanadium sodium fluorophosphate cathode material and the existing Na 3 V 2 (PO 4 ) 2 F 3 The vanadium pentoxide is used as a special vanadium source, oxalic acid is used as a reducing agent and a carbon source, pentavalent vanadium forms tetravalent vanadium under the reducing action of the oxalic acid, and the pentavalent vanadium is continuously mixed with ammonium dihydrogen phosphate, sodium fluoride and ethylene glycol to obtain a trivalent vanadium solution.
The inventors believe that Na is obtained in the prior art 3 V 2 (PO 4 ) 2 F 3 The particles are usually of a particle structure on a microscopic scale, and the improvement of the electrochemical performance is very unfavorable due to the large size of the particles. The nano structure can shorten the diffusion distance of sodium ions and electrons and improve the kinetic process of sodium ion deintercalation. Through continuous exploration, the inventor finds that a special vanadium sodium fluorophosphate nanosheet structure can be formed by controlling specific raw materials and specific reaction conditions.
The two-dimensional nanosheet structure can better adapt to volume change generated in the sodium ion deintercalation process, the structural stability of the electrode material is improved, the gaps among the nanosheets are beneficial to permeation of electrolyte, and the cycle performance and the rate capability of the material can be better improved. However, the nanostructures are prone to agglomeration during cycling, making long cycling stability difficult to achieve.
In the invention, a unique reaction system is constructed in a solvothermal environment, so that the surface of the sodium vanadium fluorophosphate nanosheet is coated with a carbon layer, the conductivity of the sodium vanadium fluorophosphate nanosheet is improved, and the nanosheets are self-assembled to form nano micro-columns in the environment of the presence of the carbon nanotube with high conductivity and are uniformly dispersed in the three-dimensional network structure of the carbon nanotube, so that not only is the conductivity of a single sodium vanadium fluorophosphate nanosheet improved, but also the conductivity between the sodium vanadium fluorophosphate nano-micro-columns is effectively improved, and the conductivity of the whole material is greatly improved. More importantly, the whole structure is obtained by taking the three-dimensional network of the carbon nano tube as a support and taking the sodium vanadium fluorophosphate nano micro-column as a filling material inside, so that the structure collapse phenomenon of the material in the circulating process is reduced to the maximum extent, and the specific capacity, the circulating performance and the rate capability of the material are greatly improved.
The specific scheme is as follows:
a preparation method of a sodium vanadium fluorophosphate nanocomposite material comprises the following steps:
(1) Dissolving vanadium pentoxide and oxalic acid in deionized water to obtain a tetravalent vanadium solution;
(2) Mixing the tetravalent vanadium solution obtained in the step (1) with ammonium dihydrogen phosphate, sodium fluoride and ethylene glycol to obtain a trivalent vanadium solution;
(3) Mixing the carbon nano tube with the trivalent vanadium solution obtained in the step (2), stirring and uniformly dispersing to obtain a mixed solution;
(4) Carrying out solvothermal reaction on the mixed solution obtained in the step (3), filtering, washing and drying after the reaction is finished, so as to obtain a sodium vanadium fluorophosphate nano composite material;
the sodium vanadium fluorophosphate nanocomposite is of a three-dimensional continuous network structure, wherein the sodium vanadium fluorophosphate is of a nanosheet structure, the width of a single sodium vanadium fluorophosphate nanosheet is 100-300 nanometers, the thickness of the single sodium vanadium fluorophosphate nanosheet is 1-10 nanometers, a layer of hydrothermal carbon is coated on the surface of the single sodium vanadium fluorophosphate nanosheet, and the sodium vanadium fluorophosphate nanosheets are assembled into a microcolumn structure along a direction perpendicular to the surface of the layer; the carbon nano tubes are alternately stacked to form a three-dimensional conductive network, the sodium vanadium fluorophosphate micro-pillars are dispersed in the three-dimensional conductive network, and the three-dimensional conductive network connects a plurality of the sodium vanadium fluorophosphate micro-pillars.
Further, in the step (1), the molar ratio of vanadium pentoxide to oxalic acid is 1:2-4; oxalic acid is used as a reducing agent and a carbon source for hydrothermal reaction; preferably, the concentration of the tetravalent vanadium solution is 0.1-1mol/L.
Further, in the step (2), the molar ratio of ammonium dihydrogen phosphate to sodium fluoride is 1-2:2-3;
optionally, the molar ratio of the sodium fluoride in the step (2) to the vanadium pentoxide in the step (1) is 2-3:0.1 to 1;
optionally, ethylene glycol is used as a reducing agent to reduce tetravalent vanadium into trivalent vanadium, and is used as a structure guiding agent in the solvothermal reaction process in the step (4) to promote the material to form a micro-column structure formed by stacking nanosheets, and preferably, the volume ratio of the ethylene glycol to the deionized water in the step (1) is 2-10: 1.
further, in the step (3), the amount of the carbon nano tube is 2wt% -10wt% of the total weight of the sodium vanadium fluorophosphate composite material;
preferably, the carbon nano tube is dispersed in deionized water to obtain a carbon nano tube dispersion liquid with the concentration of 1-10mg/ml, and then the carbon nano tube dispersion liquid is added into the trivalent vanadium solution obtained in the step (2), and ultrasonic dispersion is carried out to obtain a mixed solution.
Further, in the step (4), the temperature of the solvothermal reaction is 120-200 ℃ and the time is 2-24h;
preferably, the temperature of the solvothermal reaction is 140-180 ℃ and the time is 6-18h.
The invention also provides a preparation method of the sodium vanadium fluorophosphate nanocomposite, and the prepared sodium vanadium fluorophosphate nanocomposite is of a three-dimensional continuous network structure, wherein the sodium vanadium fluorophosphate is of a nanosheet structure, the width of a single sodium vanadium fluorophosphate nanosheet is 100-300 nanometers, the thickness of the single sodium vanadium fluorophosphate nanosheet is 1-10 nanometers, the surface of the single sodium vanadium fluorophosphate nanosheet is coated with a layer of hydrothermal carbon, and the sodium vanadium fluorophosphate nanosheets are assembled into a microcolumn structure along a direction perpendicular to the surface of the lamella; the carbon nano tubes are alternately stacked to form a three-dimensional conductive network, the sodium vanadium fluorophosphate micro-columns are dispersed in the three-dimensional conductive network, and the three-dimensional conductive network connects the plurality of sodium vanadium fluorophosphate micro-columns.
Further, the specific discharge capacity of the sodium vanadium fluorophosphate nano composite material is more than or equal to 110mAh g when the sodium vanadium fluorophosphate nano composite material is charged and discharged by 0.2C -1 After 200 times of circulation, the capacity retention rate is more than or equal to 92 percent.
The invention also protects the application of the sodium vanadium fluorophosphate nanocomposite in a sodium ion battery.
The invention also protects an electrode comprising the sodium vanadium fluorophosphate composite material.
The invention also provides a sodium ion battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode is the electrode.
Has the advantages that:
the vanadium sodium fluorophosphate nano composite material prepared by the one-step solvothermal method has a three-dimensional continuous network structure, wherein Na 3 V 2 (PO 4 ) 2 F 3 The nano sheets can shorten the diffusion and electronic transmission distance of sodium ions, better adapt to the volume change generated in the process of sodium ion deintercalation, improve the structural stability of the electrode material, facilitate the permeation of electrolyte through gaps among the nano sheets, and improve the high-rate charge and discharge performance of the material; na (Na) 3 V 2 (PO 4 ) 2 F 3 The carbon layer coated on the surface of the nano sheet is beneficial to improving Na 3 V 2 (PO 4 ) 2 F 3 Conductivity of the nanosheets; na (Na) 3 V 2 (PO 4 ) 2 F 3 The microcolumn formed by stacking the nanosheets layer by layer is beneficial to improving the structural stability of the nanosheets; the three-dimensional conductive network structure formed by the CNTs with high conductivity is beneficial to preventing Na 3 V 2 (PO 4 ) 2 F 3 The agglomeration of the microcolumns improves the stability of the nano structure and further improves Na 3 V 2 (PO 4 ) 2 F 3 Electrical conductivity between the microcolumns.
In a word, the vanadium sodium fluorophosphate nanocomposite prepared by the invention shows a discharge specific capacity close to a theoretical specific capacity, excellent cycle performance and rate capability, and has wide application prospect in the field of sodium ion batteries.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is an XRD pattern of samples prepared according to example 1 and comparative example 1 provided by the present invention;
FIG. 2 is an SEM image of a sample prepared according to example 1 provided by the present invention;
FIG. 3 is an SEM image of a sample prepared in comparative example 1 provided by the present invention;
FIG. 4 is a TEM image provided by the present invention, wherein FIGS. 4 (a) and 4 (b) are TEM images of sodium vanadium fluorophosphate nanocomposites at different magnifications, illustrating that the width of the sodium vanadium fluorophosphate nanosheets is 100-300 nm and the thickness is 1-10 nm, and the nanosheets are stacked layer by layer into nanocolumns dispersed in a three-dimensional conductive network structure formed by carbon nanotubes; FIGS. 4 (c) - (j) are maps of the elements of sodium vanadium fluorophosphate nanocomposites;
FIG. 5 is a graph of the cycle performance of samples prepared in example 1, comparative example 1 and comparative example 3 provided by the present invention;
fig. 6 is a graph of rate capability of samples prepared in example 1, comparative example 1 and comparative example 2 provided by the present invention.
Detailed Description
The preparation method of the sodium vanadium fluorophosphate composite material comprises the following steps:
(1) Dissolving vanadium pentoxide and oxalic acid in deionized water to obtain a tetravalent vanadium solution;
(2) Mixing the tetravalent vanadium solution obtained in the step (1) with ammonium dihydrogen phosphate, sodium fluoride and ethylene glycol to obtain a trivalent vanadium solution;
(3) Mixing the carbon nano tube with the trivalent vanadium solution obtained in the step (2), stirring and uniformly dispersing to obtain a mixed solution;
(4) And (4) carrying out solvothermal reaction on the mixed solution obtained in the step (3), filtering and washing after the reaction is finished, and obtaining the sodium vanadium fluorophosphate nano composite material.
In the step (1), the molar ratio of vanadium pentoxide to oxalic acid is 1:2-4, preferably 1:3, oxalic acid is used as a reducing agent and a carbon source; the concentration of the tetravalent vanadium solution is 0.1-1mol/L, preferably 0.2-0.8 mol/L, more preferably 0.5mol/L and 0.6mol/L.
In the step (2), the molar ratio of ammonium dihydrogen phosphate to sodium fluoride is 1-2:2-3, preferably 2:3; the molar ratio of the sodium fluoride in the step (2) to the vanadium pentoxide in the step (1) is 2-3:0.1 to 1, preferably 3:1.
in the step (2), the ethylene glycol not only serves as a reducer of tetravalent vanadium to reduce the tetravalent vanadium into trivalent vanadium, but also serves as a structure guiding agent in the subsequent solvothermal reaction process to obtain Na 3 V 2 (PO 4 ) 2 F 3 The nano sheets are stacked layer by layer to form a special shape. And other materials such as ethanol, isopropanol, polyethylene glycol-400 and the like cannot play the roles of reducing agent and structure guiding at the same time, and the vanadium sodium fluorophosphate nano composite material obtained by the invention cannot be obtained.
Preferably, the volume ratio of the ethylene glycol to the deionized water in the step (1) is 2-10: 1, more preferably 4 to 6:1, the concentration of the reaction system influences the formation of the nano-sheet, thereby influencing the electrochemical performance of the material.
In the step (3), the amount of the carbon nano tube is 2wt% -10wt% of the total weight of the sodium vanadium fluorophosphate nano composite material, and is preferably 4wt% -7wt%. In order to ensure that the material is uniformly dispersed, preferably, the carbon nanotube is dispersed in deionized water to obtain a carbon nanotube dispersion liquid with the concentration of 1-10mg/ml, and then the carbon nanotube dispersion liquid is added into the trivalent vanadium solution obtained in the step (2), and ultrasonic dispersion is carried out to obtain a mixed solution.
In the step (4), the temperature of the solvothermal reaction is 120-200 ℃ and the time is 2-24h. Preferably, the temperature of the solvothermal reaction is 140-180 ℃ and the time is 6-18h. For example 150 ℃,160 ℃ or 170 ℃.
In the present invention, the source of each raw material such as carbon nanotubes is not particularly limited, and it can be obtained commercially. The method for mixing the solution, the method for dispersing, the device for hydrothermal reaction and the heating method are not particularly limited, as long as the reaction temperature in the sealed system is 120-200 ℃ and the expected reaction time is ensured. For example, a hydrothermal reaction kettle can be used, which is known to those skilled in the art and will not be described herein.
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 15mL of deionized water to obtain a dark blue solution which is a tetravalent vanadium solution; adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio into a tetravalent vanadium solution, stirring and dissolving, adding 100mL of glycol, and stirring to obtain a green solution which is a trivalent vanadium solution; will be according to the final Na 3 V 2 (PO 4 ) 2 F 3 Performing ultrasonic dispersion on 5wt% carbon nanotubes in CNTs in 10mL deionized water to obtain a carbon nanotube dispersion liquid; adding the carbon nano tube dispersion liquid into the green solution, stirring and mixing, carrying out ultrasonic treatment for 0.5h, then pouring into a 200mL polytetrafluoroethylene inner container, putting the reaction kettle into an oven, reacting for 12h at 170 ℃, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain Na with a three-dimensional continuous network structure 3 V 2 (PO 4 ) 2 F 3 @ C/CNTs nanocomposites.
Comparative example 1
On the basis of example 1, a comparative material Na was prepared without adding carbon nanotubes 3 V 2 (PO 4 ) 2 F 3 . The method comprises the following specific steps:
heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 25mL of deionized water to obtain a dark blue solution, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving, adding 100mL of ethylene glycol to obtain a green solution, stirring and mixing, pouring into a 200mL of polytetrafluoroethylene inner container, putting a reaction kettle into an oven to react for 12 hours at 170 ℃, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain vanadium sodium fluorophosphate.
XRD analysis was performed on the materials prepared in example 1 and comparative example 1, respectively, and as shown in FIG. 1, it can be seen that after the sodium vanadium fluorophosphate was compounded with the carbon nanotube, the half height width of the diffraction peak of the obtained composite material was increased, indicating that the grain size was decreased.
SEM analysis is performed on the materials prepared in example 1 and comparative example 1, respectively, and FIG. 2 shows the morphology of the composite material obtained in example 1, and it can be seen that Na having a three-dimensional continuous network structure 3 V 2 (PO 4 ) 2 F 3 The @ C/CNTs nano composite material is made of carbon nano tube and Na 3 V 2 (PO 4 ) 2 F 3 The method comprises the following steps of @ C microcolumns, alternately stacking carbon nano tubes in a three-dimensional continuous network structure to form a three-dimensional conductive network, coating a carbon layer on the surface of a sodium vanadium fluorophosphate nanosheet, and superposing the carbon layer one by one to form the sodium vanadium fluorophosphate microcolumns, uniformly dispersing the sodium vanadium fluorophosphate microcolumns in the three-dimensional conductive network, and connecting the multiple sodium vanadium fluorophosphate microcolumns by the three-dimensional conductive network.
Fig. 3 shows the morphology obtained in comparative example 1, and it is possible to see an obvious agglomeration phenomenon, where the material also has sodium vanadium fluorophosphate nanosheets, the width of the nanosheets is about 500nm, and the sodium vanadium fluorophosphate nanosheets are stacked together, which means that the specific surface of the material is small, and is difficult to fully contact with an electrolyte in the charging and discharging process, and the hydrothermal carbon coated on the surface has a limited improvement in conductivity, resulting in poor cycle performance and rate capability.
FIG. 4 is a TEM image of the composite obtained in example 1, wherein FIGS. 4 (a) and 4 (b) are TEM images of sodium vanadium fluorophosphate nanocomposites at different magnifications, and FIGS. 4 (c) - (j) are elemental maps of the sodium vanadium fluorophosphate nanocomposites, specifically, the sodium vanadium fluorophosphate has a nanosheet structure, the width of a single sodium vanadium fluorophosphate nanosheet is 100-300 nm, the thickness is 1-10 nm, the surface of the nanosheet is coated with a carbon layer, and the sodium vanadium fluorophosphate nanosheets are arranged along a direction perpendicular to the surface of the lamellaAssembling into a micro-column structure; three-dimensional conductive network structure formed by carbon nanotubes is prepared by reacting Na 3 V 2 (PO 4 ) 2 F 3 The @ C microcolumn structures are connected.
Example 2
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 25mL of deionized water to obtain a dark blue solution, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving, adding 150mL of ethylene glycol, and stirring to obtain a green solution; will be according to the final Na 3 V 2 (PO 4 ) 2 F 3 Performing ultrasonic dispersion on 3wt% of carbon nanotubes in CNTs in 10mL of deionized water to obtain a carbon nanotube dispersion liquid; adding the carbon nano tube dispersion liquid into the green solution, stirring and mixing, carrying out ultrasonic treatment for 1h, then pouring into a 200mL polytetrafluoroethylene inner container, putting the reaction kettle into an oven, reacting for 12h at 170 ℃, cooling to room temperature, carrying out suction filtration, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying at 60 ℃ to obtain Na with a three-dimensional continuous network structure 3 V 2 (PO 4 ) 2 F 3 @ C/CNTs nanocomposite.
Example 3
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 20mL of deionized water to obtain a dark blue solution, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving, adding 150mL of ethylene glycol, and stirring to obtain a green solution; ultrasonically dispersing CNTs with the mass fraction of 10% in 20mL of deionized water to obtain a dispersion liquid; adding the dispersion into the green solution, stirring and mixing, carrying out ultrasonic treatment for 1h, then pouring into a 200mL polytetrafluoroethylene inner container, putting the reaction kettle into an oven for reacting for 12h at 170 ℃, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain Na with a three-dimensional continuous network structure 3 V 2 (PO 4 ) 2 F 3 @ C/CNTs nanocomposite.
Example 4
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 15mL of deionized water to obtain a dark blue solution, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring for dissolving, and adding 100mL of ethylene glycolStirring to obtain a green solution; ultrasonically dispersing CNTs with the mass fraction of 5% in 10mL of deionized water to obtain a dispersion liquid; adding the dispersion into the green solution, stirring and mixing, carrying out ultrasonic treatment for 0.5h, then pouring into a 200mL polytetrafluoroethylene inner container, putting the reaction kettle into an oven, reacting for 6h at 180 ℃, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 80 ℃ to obtain Na with a three-dimensional continuous network structure 3 V 2 (PO 4 ) 2 F 3 @ C/CNTs nanocomposite.
Example 5: electrochemical Performance test
Na of three-dimensional continuous network structure prepared in example 1 3 V 2 (PO 4 ) 2 F 3 The @ C/CNTs nanocomposite and acetylene black and polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 7. Metal sodium sheet as negative electrode, whatman glass fiber as separator, 1M NaClO dissolved in ethylene carbonate/dimethyl carbonate (EC/DMC) (1, volume ratio) and 5% fluoroethylene carbonate (FEC) added 4 As an electrolyte, a button cell (model 2025) was assembled in a glove box (Mikrouna, MKSS 1-1305-0838) filled with high-purity argon gas. The charging and discharging performance test is carried out on a blue test system with the type CT 2001A produced in Wuhan, and the test voltage range is 2.5-4.3V (reference is Na) + /Na)。
As shown in FIG. 5, na is present when charging and discharging are carried out at 0.2C 3 V 2 (PO 4 ) 2 F 3 @ C/CNTs nanocomposite exhibits 116mAh g -1 After the discharge specific capacity of (2) is cycled for 200 times, the capacity retention rate is 92%.
As shown in FIG. 6, the sandwich structure Na was charged and discharged at 0.2C, 0.5C, 1C, 2C, 5C and 10C, respectively 3 V 2 (PO 4 ) 2 F 3 @ C/CNTs nanocomposites achieved 114, 106, 96, 88, 80 and 68mAh g, respectively -1 Specific discharge capacity of (2).
Comparative example 2
And mixing the product prepared in the comparative example 1 with carbon nanotubes in a mass ratio of 95. Referring to example 5, a battery was prepared and tested for electrochemical properties under the same conditions.
As shown in FIG. 6, the comparative composite 2 obtained 94, 84, 75, 59, 43, and 24mAh g when charged and discharged at 0.2C, 0.5C, 1C, 2C, 5C, and 10C, respectively -1 The specific discharge capacity of the material is significantly lower than that of the material prepared in example 1, which indicates that Na cannot be effectively combined by adopting a ball milling mode 3 V 2 (PO 4 ) 2 F 3 And carbon nanotubes, the specific capacity of the material is lower.
Comparative example 3
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 25mL of deionized water to obtain a dark blue solution, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving, adding 100mL of ethylene glycol to obtain a green solution, adding 0.3g of sucrose, stirring and mixing, pouring into a 200mL of polytetrafluoroethylene inner container, placing a reaction kettle in an oven to react for 12 hours at 170 ℃, cooling to room temperature, carrying out suction filtration, washing 3 times with deionized water and absolute ethyl alcohol respectively, and drying at 60 ℃ to obtain a comparative composite material 3. Referring to example 5, a battery was prepared and tested for electrochemical performance under the same conditions.
As shown in FIG. 5, the first discharge specific capacity of comparative composite 3 prepared in comparative example 3 was 52mAh g -1 After 200 times of circulation, the specific discharge capacity is 41mAh g -1 It is shown that the specific capacity and the cycle performance of the product are greatly reduced after the carbon nano tube is replaced by the conventional carbon source sucrose.
Comparative example 4
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 25mL of deionized water to obtain a dark blue solution, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving, adding 100mL of ethanol, stirring for 10 minutes to obtain a blue sol, adding 62.5mg of carbon nano tube dispersion, uniformly dispersing, pouring into a 200mL polytetrafluoroethylene inner container, putting a reaction kettle into an oven, reacting for 12 hours at 170 ℃, cooling to room temperature, performing suction filtration, washing 3 times with deionized water and absolute ethanol respectively, and drying at 60 ℃ to obtain the vanadium sodium fluorophosphate composite material.
Comparative example 5
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 25mL of deionized water to obtain a dark blue solution, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving, adding 100mL of isopropanol, stirring, mixing, adding 62.5mg of carbon nanotube dispersion liquid, uniformly dispersing, pouring into a 200mL of polytetrafluoroethylene inner container, putting a reaction kettle into an oven for reacting at 170 ℃ for 12 hours, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain the vanadium sodium fluorophosphate composite material.
Comparative example 6
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of oxalic acid in 25mL of deionized water to obtain a dark blue solution, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving, then adding 100mL of polyethylene glycol-400, stirring, mixing, adding 62.5mg of carbon nanotube dispersion liquid, uniformly dispersing, pouring into a 200mL of polytetrafluoroethylene inner container, putting a reaction kettle into an oven, reacting at 170 ℃ for 12h, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain the vanadium sodium fluorophosphate composite material.
Comparative example 7
Heating and dissolving 3mmol of vanadium pentoxide and 9mmol of ascorbic acid in 25mL of deionized water, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving, adding 100mL of ethylene glycol, stirring and mixing, adding 62.5mg of carbon nano tube dispersion liquid, uniformly dispersing, pouring into a 200mL polytetrafluoroethylene inner container, placing a reaction kettle in an oven, reacting for 12 hours at 170 ℃, cooling to room temperature, performing suction filtration, washing 3 times with deionized water and absolute ethyl alcohol respectively, and drying at 60 ℃ to obtain the vanadium sodium fluorophosphate composite material.
Comparative example 8
Heating and dissolving 3mmol of ammonium metavanadate and 6mmol of citric acid in 25mL of deionized water, adding ammonium dihydrogen phosphate and sodium fluoride in a stoichiometric ratio, stirring and dissolving to obtain a solution, adding 100mL of ethylene glycol, stirring and mixing, adding 62.5mg of carbon nanotube dispersion, uniformly dispersing, pouring into a 200mL polytetrafluoroethylene inner container, placing a reaction kettle in an oven for reacting at 170 ℃ for 12 hours, cooling to room temperature, carrying out suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain the vanadium sodium fluorophosphate composite material.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. A preparation method of a sodium vanadium fluorophosphate nanocomposite is characterized by comprising the following steps: the method comprises the following steps:
(1) Dissolving vanadium pentoxide and oxalic acid in deionized water to obtain a tetravalent vanadium solution; the molar ratio of the vanadium pentoxide to the oxalic acid is 1:2-4; oxalic acid is used as a reducing agent and a carbon source for hydrothermal reaction;
(2) Mixing the tetravalent vanadium solution obtained in the step (1) with ammonium dihydrogen phosphate, sodium fluoride and ethylene glycol to obtain a trivalent vanadium solution; the volume ratio of the ethylene glycol to the deionized water in the step (1) is 2 to 10:1;
(3) Mixing the carbon nano tube with the trivalent vanadium solution obtained in the step (2), stirring and uniformly dispersing to obtain a mixed solution;
(4) Carrying out solvothermal reaction on the mixed solution obtained in the step (3), wherein the temperature of the solvothermal reaction is 120-200 ℃, the time is 2-24h, and filtering, washing and drying after the reaction is finished to obtain a sodium vanadium fluorophosphate nano composite material; the ethylene glycol is used as a reducing agent to reduce tetravalent vanadium into trivalent vanadium, and is used as a structure guiding agent in the solvothermal reaction process in the step (4) to promote materials to form a micro-column structure formed by stacking nanosheets;
the sodium vanadium fluorophosphate nanocomposite is of a three-dimensional continuous network structure, wherein the sodium vanadium fluorophosphate is of a nanosheet structure, the width of a single sodium vanadium fluorophosphate nanosheet is 100-300 nanometers, the thickness of the single sodium vanadium fluorophosphate nanosheet is 1-10 nanometers, the surface of the single sodium vanadium fluorophosphate nanosheet is coated with a layer of hydrothermal carbon, and the sodium vanadium fluorophosphate nanosheets are assembled into a microcolumn structure along a direction perpendicular to the surface of the sheet layer; the carbon nano tubes are alternately stacked to form a three-dimensional conductive network, the sodium vanadium fluorophosphate micro-pillars are dispersed in the three-dimensional conductive network, and the three-dimensional conductive network connects a plurality of the sodium vanadium fluorophosphate micro-pillars.
2. The method for preparing the sodium vanadium fluorophosphate nanocomposite according to claim 1, characterized in that: in the step (1), the concentration of the tetravalent vanadium solution is 0.1-1mol/L.
3. The method for preparing sodium vanadium fluorophosphate nanocomposites according to claim 1 or 2, characterized in that: in the step (2), the molar ratio of ammonium dihydrogen phosphate to sodium fluoride is 1-2:2-3.
4. The method for preparing sodium vanadium fluorophosphate nanocomposites according to claim 1 or 2, characterized in that: the molar ratio of the sodium fluoride in the step (2) to the vanadium pentoxide in the step (1) is 2-3:0.1-1.
5. The method for preparing sodium vanadium fluorophosphate nanocomposites according to claim 1, characterized in that: in the step (3), the amount of the carbon nano tube is 2wt% -10wt% of the total weight of the sodium vanadium fluorophosphate composite material.
6. The method for preparing sodium vanadium fluorophosphate nanocomposites according to claim 5, wherein: and (3) dispersing the carbon nano tube in deionized water to obtain a carbon nano tube dispersion liquid with the concentration of 1-10mg/mL, adding the carbon nano tube dispersion liquid into the trivalent vanadium solution obtained in the step (2), and performing ultrasonic dispersion to obtain a mixed solution.
7. The method for preparing sodium vanadium fluorophosphate nanocomposites according to claim 1 or 5, wherein: in the step (4), the temperature of the solvothermal reaction is 140-180 ℃ and the time is 6-18h.
8. The sodium vanadium fluorophosphate nanocomposite prepared by the method for preparing a sodium vanadium fluorophosphate nanocomposite according to any one of claims 1 to 7, which is characterized in that: the sodium vanadium fluorophosphate nanocomposite is of a three-dimensional continuous network structure, wherein the sodium vanadium fluorophosphate is of a nanosheet structure, the width of a single sodium vanadium fluorophosphate nanosheet is 100-300 nanometers, the thickness of the single sodium vanadium fluorophosphate nanosheet is 1-10 nanometers, a layer of hydrothermal carbon is coated on the surface of the single sodium vanadium fluorophosphate nanosheet, and the sodium vanadium fluorophosphate nanosheets are assembled into a microcolumn structure along a direction perpendicular to the surface of the layer; the carbon nano tubes are alternately stacked to form a three-dimensional conductive network, the sodium vanadium fluorophosphate micro-columns are dispersed in the three-dimensional conductive network, and the three-dimensional conductive network connects the plurality of sodium vanadium fluorophosphate micro-columns.
9. The sodium vanadium fluorophosphate nanocomposite material according to claim 8, wherein: the specific discharge capacity is more than or equal to 110mAh g when charging and discharging are carried out by 0.2C -1 And after the circulation is carried out for 200 times, the capacity retention rate is more than or equal to 92 percent.
10. Use of the sodium vanadium fluorophosphate nanocomposite according to claim 8 or 9 in a sodium-ion battery.
11. An electrode comprising the sodium vanadium fluorophosphate nanocomposite according to claim 8 or 9.
12. A sodium ion battery comprising a positive electrode, a negative electrode and an electrolyte, characterized in that: the positive electrode is the electrode according to claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111301879.XA CN114031063B (en) | 2021-11-04 | 2021-11-04 | Sodium vanadium fluorophosphate nanocomposite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111301879.XA CN114031063B (en) | 2021-11-04 | 2021-11-04 | Sodium vanadium fluorophosphate nanocomposite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114031063A CN114031063A (en) | 2022-02-11 |
| CN114031063B true CN114031063B (en) | 2023-02-28 |
Family
ID=80142845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111301879.XA Active CN114031063B (en) | 2021-11-04 | 2021-11-04 | Sodium vanadium fluorophosphate nanocomposite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114031063B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159493A (en) * | 2022-07-15 | 2022-10-11 | 西北工业大学 | Preparation method of sodium vanadium fluorophosphate cathode material, battery cathode and battery |
| CN115650201B (en) * | 2022-12-26 | 2023-03-10 | 山东海科创新研究院有限公司 | Preparation method of lithium difluorophosphate |
| CN117239101A (en) * | 2023-11-10 | 2023-12-15 | 临沂大学 | Nitrogen-doped carbon nanotube-coated polyanion type positive electrode material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898752A (en) * | 2017-03-31 | 2017-06-27 | 中南大学 | A kind of porous spherical vanadium phosphate sodium/carbon pipe composite positive pole and preparation method thereof |
| WO2017124439A1 (en) * | 2016-01-18 | 2017-07-27 | 武汉理工大学 | Three-dimensional na3v2(po4)3 nanowire network electrode material, preparation method therefor and use thereof |
| CN108365199A (en) * | 2018-02-11 | 2018-08-03 | 西北工业大学 | Carbon-coated fluorophosphoric acid vanadium potassium carbon nano tube compound material and preparation method and application |
| CN108682855A (en) * | 2018-05-28 | 2018-10-19 | 苏州大学 | A kind of method of controllable preparation fluorophosphoric acid vanadium sodium positive electrode |
| CN109841800A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of fluorophosphoric acid vanadium sodium and carbon complex and its preparation and application |
| RU2747565C1 (en) * | 2020-05-21 | 2021-05-07 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела и механохимии Сибирского отделения Российской академии наук | Method of obtaining composite cathode material based on na3v2 (po4)2f3 for sodium-ion batteries |
-
2021
- 2021-11-04 CN CN202111301879.XA patent/CN114031063B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017124439A1 (en) * | 2016-01-18 | 2017-07-27 | 武汉理工大学 | Three-dimensional na3v2(po4)3 nanowire network electrode material, preparation method therefor and use thereof |
| CN106898752A (en) * | 2017-03-31 | 2017-06-27 | 中南大学 | A kind of porous spherical vanadium phosphate sodium/carbon pipe composite positive pole and preparation method thereof |
| CN109841800A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of fluorophosphoric acid vanadium sodium and carbon complex and its preparation and application |
| CN108365199A (en) * | 2018-02-11 | 2018-08-03 | 西北工业大学 | Carbon-coated fluorophosphoric acid vanadium potassium carbon nano tube compound material and preparation method and application |
| CN108682855A (en) * | 2018-05-28 | 2018-10-19 | 苏州大学 | A kind of method of controllable preparation fluorophosphoric acid vanadium sodium positive electrode |
| RU2747565C1 (en) * | 2020-05-21 | 2021-05-07 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела и механохимии Сибирского отделения Российской академии наук | Method of obtaining composite cathode material based on na3v2 (po4)2f3 for sodium-ion batteries |
Non-Patent Citations (2)
| Title |
|---|
| 碳包覆对水系磷酸钛钠电化学性能的影响;赵平等;《现代化工》;20161220(第12期);第70-73页 * |
| 钠离子电池负极材料研究进展;晏然等;《节能技术》;20161126(第06期);第516-520页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114031063A (en) | 2022-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Prussian blue analogs cathodes for aqueous zinc ion batteries | |
| CN114031063B (en) | Sodium vanadium fluorophosphate nanocomposite and preparation method thereof | |
| Wang et al. | Cornlike ordered N-doped carbon coated hollow Fe3O4 by magnetic self-assembly for the application of Li-ion battery | |
| Deng et al. | Hydrothermal-assisted synthesis of the Na 7 V 4 (P 2 O 7) 4 (PO 4)/C nanorod and its fast sodium intercalation chemistry in aqueous rechargeable sodium batteries | |
| TWI664774B (en) | Anode of lithium-ion battery and flexible lithium-ion battery using the same | |
| Gong et al. | In-situ synthesis of monodisperse micro-nanospherical LiFePO4/carbon cathode composites for lithium-ion batteries | |
| Lu et al. | Cobalt-doped Zn 2 GeO 4 nanorods assembled into hollow spheres as high-performance anode materials for lithium-ion batteries | |
| Bai et al. | Hierarchical 3D micro-/nano-V2O5 (vanadium pentoxide) spheres as cathode materials for high-energy and high-power lithium ion-batteries | |
| WO2010150857A1 (en) | Composite nano porous electrode material, process for production thereof, and lithium ion secondary battery | |
| KR101684645B1 (en) | A nano-composite of V2O5 xerogel and carbon, and cathode for rechargeable lithium sulfur battery comprising the same, and preparation process thereof | |
| CN105226267B (en) | Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application | |
| Dou et al. | Template-free synthesis of porous V2O5 yolk-shell microspheres as cathode materials for lithium ion batteries | |
| Su et al. | Template-assisted formation of porous vanadium oxide as high performance cathode materials for lithium ion batteries | |
| CN104979541A (en) | Lithium titanate composite material and preparation method thereof | |
| Zhou et al. | Fabrication of nanoplate Li-rich cathode material via surfactant-assisted hydrothermal method for lithium-ion batteries | |
| CN104852040A (en) | Preparation method of lithium nickel manganese oxide anode material for high-rate lithium ion battery | |
| CN113422011A (en) | Carbon nanotube-in-tube @ manganese dioxide nanosheet composite material and preparation and application thereof | |
| CN110467170B (en) | High-potential positive electrode material of potassium ion battery and preparation method thereof | |
| Luo et al. | N-Doped graphitic ladder-structured carbon nanotubes as a superior sulfur host for lithium–sulfur batteries | |
| Hou et al. | Li-rich layered oxide microspheres prepared by the biomineralization as high-rate and cycling-stable cathode for Li-ion batteries | |
| Song et al. | Significantly improved high-rate Li-ion batteries anode by encapsulating tin dioxide nanocrystals into mesotunnels | |
| Xiong et al. | A dual-carbon structured molybdenum selenide composites controlled via interface engineering and chemical bonding to attain high initial coulombic efficiency and rate capability of potassium-ion batteries | |
| CN113506860A (en) | Carbon nanotube-in-tube @ selenium composite material and preparation method and application thereof | |
| CN112186166B (en) | Molybdenum/cobalt oxide-carbon composite material and preparation method thereof, lithium ion battery negative electrode piece and lithium ion battery | |
| CN109980221A (en) | A kind of anode material for high-voltage lithium ion and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |