CN112216823B - Vanadium sodium fluorophosphate coated positive electrode material, sodium ion battery and preparation method and application of sodium vanadium fluorophosphate coated positive electrode material and sodium ion battery - Google Patents
Vanadium sodium fluorophosphate coated positive electrode material, sodium ion battery and preparation method and application of sodium vanadium fluorophosphate coated positive electrode material and sodium ion battery Download PDFInfo
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Abstract
The invention discloses a vanadium sodium fluorophosphate coated positive electrode material, a sodium ion battery, and a preparation method and application thereof. The sodium vanadium fluorophosphate-coated cathode material comprises a cathode material and a sodium vanadium fluorophosphate coating, wherein the sodium vanadium fluorophosphate coating is uniformly coated on the surface of the cathode material. The preparation method comprises the following steps: (1) reacting a mixed aqueous solution of a vanadium source, a phosphorus source, a fluorine source and a reducing agent at 25-90 ℃ to obtain a coating solution; (2) and mixing the positive electrode material with the coating liquid, and standing. When the sodium vanadium fluorophosphate-coated cathode material is used for a sodium ion battery, the cycle performance is good, and the service life is long; the preparation method has the advantages of simple process, low production cost and short production period.
Description
Technical Field
The invention relates to a vanadium sodium fluorophosphate coated positive electrode material, a sodium ion battery, and a preparation method and application thereof.
Background
With the development of renewable energy and clean energy, the demand for large-scale energy storage is generated. In order to smoothly access and fully consume renewable energy for power generation and realize optimal management and efficient utilization of energy, coordinated application of centralized energy storage, distributed energy storage and a direct-current power distribution network is required. In principle, secondary batteries suitable for large-scale energy storage applications are required to be high in safety, environmentally friendly, low in cost, abundant in resources, and have excellent electrochemical properties such as long life, high power density, and the like. The sodium ion battery technology with abundant resources and environmental friendliness becomes a hot spot of current research.
The positive electrode material is one of core parts of the sodium ion battery, and plays an important role in improving the multiplying power, specific volume, working voltage and cycling stability of the battery. Layered transition metal oxides, tunnel-shaped transition metal oxides, polyanion compounds and Prussian blue compounds are four types of sodium-ion battery positive electrode materials which are widely concerned by researchers at present.
The sodium ion battery using the prior positive electrode material of the sodium ion battery generally has poor cycle performance and can not meet the requirement of service life, especially under the condition of high temperature. In recent years, people mainly adopt technologies such as morphology regulation, carbon coating, doping and the like to modify a positive electrode material, but the cycle performance and the service life of a sodium ion battery are still to be improved.
Disclosure of Invention
The invention provides a vanadium sodium fluorophosphate coated positive electrode material, a sodium ion battery, a preparation method and application thereof, and aims to solve the problems of poor cycle performance and short service life of the conventional sodium ion battery. When the sodium vanadium fluorophosphate-coated cathode material is used for a sodium ion battery, the cycle performance is good, and the service life is long; the preparation method has the advantages of simple process, low production cost and short production period.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sodium vanadium fluorophosphate coated positive electrode material comprises a positive electrode material and a sodium vanadium fluorophosphate coating layer, wherein the sodium vanadium fluorophosphate coating layer is uniformly coated on the surface of the positive electrode material; the positive electrode material is a sodium ion battery positive electrode material stable in water; the molecular formula of the sodium vanadium fluorophosphate is Na3(VO1-xPO4)2F1+2xWherein x is more than or equal to 0 and less than or equal to 1.
In the present invention, the thickness of the sodium vanadium fluorophosphate coating layer can be more than 5nm, preferably 10 to 50nm, and more preferably 30 nm. The molecular formula of the sodium vanadium fluorophosphate is preferably Na3(VOPO4)2F。
In the present invention, the cathode material may be a sodium ion battery cathode material stable in water, which is conventional in the art, such as a transition metal oxide, a polyanion compound, a prussian blue analog, or an organic electrode material stable in water. In the invention, the term "stable in water" means that the cathode material is separated after being placed in water for a period of time, the chemical property of the cathode material is not changed, and most importantly, no sodium ions are extracted from the cathode material. After some positive electrode materials are placed in water, sodium ions in the positive electrode materials can be extracted, so that the sodium content of the materials is reduced, namely the positive electrode materials are unstable in water.
Wherein the transition metal oxide is preferably NanMnO2(0<n is less than or equal to 1). The polyanion compound is preferably a NASICON-type polyanion compound, an olivine-type polyanion compound, a phosphate-based polyanion compound, a fluorinated phosphate-based polyanion compound, or a pyrophosphate-based polyanion compound. The prussian blue analogue may have a molecular formula of NaaM[Fe(CN)6]b·cH2O, wherein M represents a transition metal, preferably Fe, Co, Ni, Mn or Zn, e.g. Na2MnFe(CN)6. The organic electrode material is preferably poly 2,2,6, 6-tetramethylpiperidinyloxy-4-vinyl ether (PTVE).
The invention also provides a preparation method of the sodium vanadium fluorophosphate coated cathode material, which comprises the following steps:
(1) reacting a mixed aqueous solution of a vanadium source, a phosphorus source, a fluorine source and a reducing agent at 25-90 ℃ to obtain a coating solution; at least one of the vanadium source, the phosphorus source and the fluorine source is a sodium salt, and the vanadium source is a pentavalent vanadium source; the reducing agent is used for adding V5+Reduction to V3+And/or V4+(ii) a The pH value of the mixed aqueous solution is 3-8; no precipitate is in the coating liquid;
(2) mixing a positive electrode material with the coating liquid, and standing; the positive electrode material is a sodium ion battery positive electrode material stable in water.
In the step (1), the reaction temperature is preferably 50 to 70 ℃, more preferably 60 ℃.
The reaction time is only required to ensure that the coating solution has no precipitate. The reaction is preferably carried out until the vanadium source reduction is complete and no precipitate has been formed. The reaction time is preferably 10 to 40min, and more preferably 20 to 30 min.
The reaction is preferably carried out under stirring. The stirring speed may be 400 to 800rpm, preferably 600 rpm.
The pH of the mixed aqueous solution is preferably 5 to 7, more preferably 6. The pH of the mixed aqueous solution can be adjusted by a conventional method, if necessary.
The molar concentration of vanadium in the mixed aqueous solution may be 0.001-0.1 mol/L, preferably 0.003-0.05 mol/L. The molar ratio of the vanadium element, the phosphorus element, the fluorine element and the sodium element in the mixed solution can be (2-2.5): 2:1: (3-6), preferably 2:2:1: 3.
The mixed aqueous solution can be prepared by a method conventional in the art, and is generally obtained by dissolving the vanadium source, the phosphorus source, the fluorine source and the reducing agent in water. The preferred preparation method of the mixed aqueous solution is as follows: dissolving the vanadium source and the reducing agent in water, and then adding the phosphorus source and the fluorine source.
Wherein the dissolution may be a routine operation in the art, typically under stirring or sonication. The stirring speed may be 400 to 800rpm, preferably 600 rpm. The power of the ultrasonic wave can be 100-500W, preferably 200-400W. The temperature of the dissolution may be 25 to 90 ℃, preferably 50 to 70 ℃, and more preferably 60 ℃.
The vanadium source may be sodium metavanadate or ammonium metavanadate, preferably sodium metavanadate. The phosphorus source may be one conventionally used in the art, and is generally one or more of phosphoric acid, sodium phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate, and preferably sodium dihydrogen phosphate. The fluorine source may be one conventionally used in the art, typically one or more of sodium fluoride, sodium hydrofluoride or ammonium fluoride, preferably sodium fluoride. The dosage of the vanadium source, the phosphorus source and the fluorine source is determined according to the molar ratio of the vanadium element, the phosphorus element, the fluorine element and the sodium element.
The reducing agent may be capable of reducing V5+Reduction to V4+And/or V3+Preferably to V4+. The reducing agent is preferably one or more of 5-hydroxymethyl-furfural-1-aldehyde (HMF), hydroxylamine, ascorbic acid, pinacol and glucose. The dosage of the reducing agent is determined according to the proportion of the number of electrons obtained and lost by the redox reaction between the reducing agent and a vanadium source.
In a preferred embodiment, the vanadium source is sodium metavanadate, the phosphorus source is sodium dihydrogen phosphate, the fluorine source is sodium fluoride, and the reducing agent is any one of glucose, ascorbic acid and hydroxylamine, preferably glucose.
In the step (2), the positive electrode material is as described above. The mass of the positive electrode material can be 10-15 times, preferably 13 times of that of vanadium.
The mixing in step (2) can be performed by a conventional method in the art, and is generally stirring, and the stirring speed can be 100-500 rpm, preferably 200-300 rpm. The mixing time is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours. The mixing temperature may be 25 to 90 ℃, preferably 50 to 70 ℃, more preferably 60 ℃. The purpose of the mixing is to uniformly distribute the positive electrode material in the coating solution.
In a preferred technical scheme, the positive electrode material is dispersed in water to form a turbid liquid, and then the turbid liquid is mixed with the coating liquid. The dispersion is preferably carried out under ultrasound. The power of the ultrasonic wave can be 200-600W, preferably 400-500W. The time of the ultrasonic treatment can be 10-40 min, preferably 20-30 min. The mass-volume ratio of the cathode material to water can be 5-20 mg/mL, preferably 10 mg/mL.
The standing may be performed at room temperature. The standing time can be 1-8 h, preferably 3-6 h. The purpose of standing is to enable the sodium vanadium fluorophosphate to precipitate out of the coating liquid and to be uniformly coated on the surface of the positive electrode material.
The water used in step (1) or (2) is water conventionally used in the art, and is typically deionized water.
In the present invention, the preparation method further comprises separation and drying. The separation can be carried out by a method conventional in the art for separating precipitates, preferably centrifugation. The drying can be carried out by drying methods customary in the art, preferably under vacuum or under a protective atmosphere. The protective atmosphere is preferably a nitrogen or argon atmosphere. The drying temperature is preferably 100 to 200 ℃. The drying time can be 6-18 h, preferably 12 h.
The invention also provides the sodium vanadium fluorophosphate coated positive electrode material prepared by the preparation method. Preferably, the sodium vanadium fluorophosphate-coated cathode material comprises a cathode material and a sodium vanadium fluorophosphate coating layer, and the sodium vanadium fluorophosphate coating layer is uniformly coated on the surface of the cathode material; the molecular formula of the sodium vanadium fluorophosphate is Na3(VO1-xPO4)2F1+2xWherein x is more than or equal to 0 and less than or equal to 1. The thickness of the sodium vanadium fluorophosphate coating layer can be more than 5nm, preferably 10-50 nm, and more preferably 30 nm.
The invention also provides a sodium-ion battery, and the positive electrode material of the sodium vanadium fluorophosphate-coated positive electrode material. The sodium ion battery can be prepared by a method conventional in the art.
The invention also provides application of the sodium vanadium fluorophosphate coated positive electrode material in a sodium-ion battery.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the invention provides a preparation method of a sodium vanadium fluorophosphate coated positive electrode material. The raw materials used in the preparation method are commercially available, the coating condition can be realized at low temperature, the coating is not required to be carried out at high temperature, and the energy consumption is greatly reduced.
(2) When the sodium vanadium fluorophosphate coated positive electrode material is used for a sodium ion battery, the sodium ion battery has good cycle performance, especially high-temperature cycle performance. The capacity retention rate is more than 80% after 500 cycles of 1C charge-discharge at 25 ℃; the capacity retention rate is more than 75% after 1C charge-discharge cycle of 200 circles at 55 ℃. Therefore, the sodium vanadium fluorophosphate-coated cathode material has a good application prospect in a sodium-ion battery.
Drawings
FIG. 1 is a HRTEM image of the material PBM @ NVOPF of example 1.
FIG. 2 is an SEM image of the material PBM @ NVOPF of example 1.
FIG. 3 is an XPS plot of the material PBM @ NVOPF of example 1.
FIG. 4 is a graph showing the comparison of charge-discharge cycle performance at 25 ℃ of sodium-ion batteries prepared from the material PBM @ NVOPF of example 1 and the material PBM of comparative example 1, wherein the voltage range is 2.0-4.0V, and the electrolyte is 1mol/L NaPF6EMC: FEC (49:49:2), and the charge-discharge current was 100 mA/g.
FIG. 5 is a graph showing the comparison of charge-discharge cycle performance at 55 ℃ of a sodium-ion battery prepared from the material PBM @ NVOPF of example 1 and the material PBM of comparative example 1, wherein the voltage range is 2.0-4.0V, and the electrolyte is 1mol/L NaPF6EMC: FEC (49:49:2), and the charge-discharge current was 100 mA/g.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
A preparation method of a sodium vanadium fluorophosphate coated cathode material comprises the following steps:
(1) 91.44mg of sodium metavanadate and 270.24mg of glucose were dissolved in 200mL of deionized water while stirring at 600rpm at 60 ℃; when the color of the solution turns deep blue, which indicates that the reduction is basically complete, 87.38mg of sodium dihydrogen phosphate and 15.38mg of sodium fluoride are added, the pH value of the obtained mixed aqueous solution is 6, and the mixed aqueous solution reacts for 20min at 60 ℃ to obtain a coating solution;
(2) 500mg of sodium manganese ferrocyanide (Na) was weighed2MnFe(CN)6Marked as PBM) is subjected to ultrasonic treatment in 50mL of deionized water for 30min, and the ultrasonic power is 500W, so as to obtain turbid liquid; pouring the turbid solution into the coating solution, stirring at 60 ℃ for 1h, and standing at room temperature for 6h to generate green precipitate;
(3) centrifuging, and drying at 200 ℃ in a vacuum atmosphere for 12h to obtain the sodium vanadium fluorophosphate coated positive electrode material which is marked as PBM @ NVOPF.
The preparation method of the sodium manganese ferrocyanide PBM comprises the following steps:
(1) weighing 0.01mol of manganese sulfate and 0.01mol of sodium ferrocyanide respectively, and dissolving the manganese sulfate and the sodium ferrocyanide respectively in 50mL of deionized water to prepare 0.2mol/L manganese sulfate solution and 0.2mol/L sodium ferrocyanide solution;
(2) weighing 0.1mol of sodium chloride, dissolving in 100mL of deionized water, and preparing into 1mol/L sodium chloride solution;
(3) placing the sodium chloride solution on a magnetic stirrer for stirring, dropwise adding the manganese sulfate solution and the sodium ferrocyanide solution into the high-speed stirred sodium chloride solution by using a peristaltic pump respectively and simultaneously, wherein a white precipitate is generated in the dropwise adding process, and the dropwise adding time is about 1.75 hours, so as to obtain a mixed solution;
(4) continuously stirring the mixed solution at room temperature for 0.5h, and then standing for 6 h;
(5) and centrifuging the mixed solution after standing to obtain a white precipitate, and drying the white precipitate at the vacuum temperature of 200 ℃ for 12h to obtain the sodium manganese hexacyanoferrate PBM.
High Resolution Transmission Electron Microscopy (HRTEM) characterization was performed using an Argonne chromatism correction-corrected TEM (ACAT) (FEI Titan 80-300ST with image Aberration corrector) with an acceleration voltage of 200 kV. Low dose HRTEM images were obtained using a Gatan direct detection camera at dose rates below 5e-/2s and High Angle Annular Dark Field (HAADF) imaging and X-ray Energy Dispersive Spectroscopy (EDS) mapping were performed by FEI Talos F200X TEM, with the results shown in fig. 1, where (a) shows the distribution of elements Na, Mn, Fe, C, N, O, P, F, and V on the surface of the material, (b) to (j) show the distribution of elements Na, Mn, Fe, C, N, O, P, F, and V, respectively, on the surface of the material, and (k) shows the distribution of elements Mn, Fe, and V on the surface of the material. As can be seen from FIG. 1(a), the NVOPF is uniformly coated on the surface of PBM, and the thickness of the coating is about 30nm as can be seen from FIG. 1 (k). In addition, SEM of the material PBM @ NVOPF is shown in FIG. 2. XPS testing showed that the element V is tetravalent in the material PBM @ NVOPF (see FIG. 3).
Comparative example 1
As a comparative material, PBM was prepared according to the preparation method of PBM as described in example 1.
Comparative example 2
91.44mg of sodium metavanadate and 270.24mg of glucose were dissolved in 200mL of deionized water while stirring at 600rpm at 100 ℃; 87.38mg of sodium dihydrogen phosphate and 15.38mg of sodium fluoride were added when the color of the solution became deep blue, and precipitation occurred soon after the addition, and no precipitate-free coating solution could be obtained.
Comparative example 3
(1) 91.44mg of sodium metavanadate and 270.24mg of glucose were dissolved in 200mL of deionized water while stirring at 600rpm at 60 ℃; when the solution turned dark blue, indicating that the reduction was substantially complete, 87.38mg of sodium dihydrogen phosphate and 15.38mg of sodium fluoride were added, and the pH of the resulting mixed aqueous solution was adjusted with H2SO4Adjusting the temperature to 2 ℃, and reacting for 20min at 60 ℃ to obtain a coating solution;
(2) 500mg of sodium manganese ferrocyanide (Na) was weighed2MnFe(CN)6Marked as PBM) is subjected to ultrasonic treatment in 50mL of deionized water for 30min, and the ultrasonic power is 500W, so as to obtain turbid liquid; pouring the turbid solution into the coating solution, stirring for 1h at 60 ℃, and then standing for 6h at room temperature, wherein no green precipitate is generated; and standing for 48 hours after continuously stirring, and generating no green precipitate and failing to successfully coat.
Comparative example 4
(1) 91.44mg of sodium metavanadate and 270.24mg of glucose were dissolved in 200mL of deionized water while stirring at 600rpm at 60 ℃; adding 87.38mg of sodium dihydrogen phosphate and 15.38mg of sodium fluoride when the color of the solution turns dark blue, wherein the pH value of the obtained mixed aqueous solution is 6, and stirring for 1h at 60 ℃;
(2) standing at room temperature for 48h to generate green precipitate;
(3) centrifuging, and drying at 200 ℃ in a vacuum atmosphere for 12h to obtain the sodium vanadium fluorophosphate material which is recorded as NVOPF.
Dispersing NVOPF in deionized water to form a coating solution; weighing 500mg PBM, and carrying out ultrasonic treatment in 50mL deionized water for 30min at the ultrasonic power of 500W to obtain a turbid solution; the turbid solution was poured into the coating solution, stirred at 60 ℃ for 1 hour, and then allowed to stand at room temperature. Visually, the white and green precipitates were separated, i.e. NVOPF was not coated onto the PBM.
Effects of the embodiment
(1) Preparation of positive pole piece of sodium ion battery
Respectively mixing the PBM @ NVOPF prepared in example 1 and the PBM prepared in comparative example 1 with conductive carbon (Super P and Ketjen black in a mass ratio of 1: 1) and polyvinylidene fluoride (PVDF) as a binder in a mass ratio of 7:2:1, adding a proper amount of 1-methyl-2-pyrrolidone (NMP) solvent to enable the mixture to be in a slurry state, stirring for 4 hours, uniformly coating the slurry on an aluminum foil, drying, punching the aluminum foil coated with black slurry into a circular pole piece with the diameter of 14mm by using a slicing machine, then tabletting by using a tabletting machine under a certain pressure, finally putting the pole piece into a vacuum oven, and drying in vacuum at 120 ℃ for 12 hours to obtain the positive pole piece of the sodium-ion battery.
(2) Preparation of sodium ion battery
The prepared positive pole piece of the sodium-ion battery is used as a working electrode, metal sodium is used as a counter electrode, and 1mol/L NaPF is used6EMC FEC (49:49:2) organic electrolyte, assembled into button cells in a glove box filled with argon atmosphere.
(3) Electrical Performance testing
The electrochemical performance of the prepared sodium-ion battery is tested by adopting a conventional method in the field, the test voltage range is 2.0-4.0V, and the test results are shown in fig. 4 and 5.
FIG. 4 is a graph comparing the 1C rate charge-discharge cycle performance at 25 ℃ of sodium ion batteries prepared from the material PBM @ NVOPF of example 1 and the material PBM of comparative example 1. Wherein the PBM @ NVOPF sodium-ion battery has the specific discharge capacity reduced from 101.5mAh/g to 85.6mAh/g after 1C multiplying power circulation for 500 circles at 25 ℃, and the capacity retention rate is 84.3%; after the PBM sodium ion battery is cycled for 500 circles at the temperature of 25 ℃ under the multiplying power of 1C, the specific discharge capacity is reduced from 105.7mAh/g to 44.4mAh/g, and the capacity retention rate is only 42.0%. Therefore, the electrochemical cycle performance of the PBM @ NVOPF material obtained after the PBM material is coated with the NVOPF material is obviously superior to that of the PBM material before coating.
FIG. 5 is a graph comparing the 1C rate charge-discharge cycle performance at 55 ℃ of sodium ion batteries prepared from the material PBM @ NVOPF of example 1 and the material PBM of comparative example 1. The discharge specific capacity of the PBM @ NVOPF material sodium ion battery is reduced from 109.5mAh/g to 86.3mAh/g after the PBM @ NVOPF material sodium ion battery is cycled for 200 circles at the temperature of 55 ℃ under the multiplying power of 1C, and the capacity retention rate is 78.8%; the specific discharge capacity of the PBM material sodium ion battery is reduced from 120.6mAh/g to 18.4mAh/g after 1C multiplying power circulation for 200 circles at 55 ℃, and the capacity retention rate is only 15.3%. Therefore, the high-temperature electrochemical cycle performance of the PBM @ NVOPF material obtained after the PBM material is coated with the NVOPF material is obviously superior to that of the PBM material before coating.
Claims (26)
1. A preparation method of a sodium vanadium fluorophosphate coated cathode material comprises the following steps:
(1) reacting a mixed aqueous solution of a vanadium source, a phosphorus source, a fluorine source and a reducing agent at 25-90 ℃ to obtain a coating solution; at least one of the vanadium source, the phosphorus source and the fluorine source is a sodium salt, and the vanadium source is a pentavalent vanadium source; the reducing agent is used for adding V5+Reduction to V4 +And/or V3+(ii) a The pH value of the mixed aqueous solution is 3-8; no precipitate is in the coating liquid;
(2) mixing a positive electrode material with the coating liquid, and standing; the positive electrode material is a sodium ion battery positive electrode material stable in water.
2. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 1, wherein in the step (1), the reaction temperature is 50-70 ℃;
and/or the reaction time is 10-40 min;
and/or the pH value of the mixed aqueous solution is 5-7;
and/or the molar concentration of the vanadium element in the mixed water solution is 0.001-0.1 mol/L; the molar ratio of vanadium element, phosphorus element, fluorine element and sodium element in the mixed water solution is (2-2.5): 2:1: (3-6);
and/or the preparation method of the mixed aqueous solution comprises the following steps: dissolving the vanadium source and the reducing agent in water, and then adding the phosphorus source and the fluorine source.
3. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 2, wherein in the step (1), the reaction temperature is 60 ℃;
and/or the reaction time is 20-30 min;
and/or the pH of the mixed aqueous solution is 6.
4. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 2, wherein in the step (1), the molar concentration of the vanadium element in the mixed aqueous solution is 0.003-0.05 mol/L;
and/or the molar ratio of the vanadium element, the phosphorus element, the fluorine element and the sodium element in the mixed aqueous solution is 2:2:1: 3.
5. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 1, wherein in the step (1), the vanadium source is sodium metavanadate or ammonium metavanadate;
and/or the phosphorus source is one or more of phosphoric acid, sodium phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate;
and/or the fluorine source is one or more of sodium fluoride, sodium hydrofluoride or ammonium fluoride;
and/or the reducing agent is one or more of 5-hydroxymethyl-furfural-1-aldehyde, hydroxylamine, ascorbic acid, pinacol and glucose;
and/or the vanadium source is sodium metavanadate; the phosphorus source is sodium dihydrogen phosphate; the fluorine source is sodium fluoride; the reducing agent is any one of glucose, ascorbic acid and hydroxylamine.
6. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 5, wherein in the step (1), the vanadium source is sodium metavanadate;
and/or the phosphorus source is sodium dihydrogen phosphate;
and/or the fluorine source is sodium fluoride;
and/or the reducing agent is glucose.
7. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 1, wherein the mass of the cathode material in the step (2) is 10 to 15 times of the mass of the vanadium element; and/or, the positive electrode material of the sodium-ion battery in the step (2) is a transition metal oxide, a polyanion compound, a Prussian blue analogue or an organic electrode material;
and/or, the mixing in the step (2) is stirring, and the stirring speed is 100-500 rpm; the mixing temperature is 25-90 ℃;
and/or, in the step (2), the positive electrode material is dispersed in water to form a turbid liquid, and then the turbid liquid is mixed with the coating liquid;
and/or, the standing in the step (2) is carried out at room temperature; the standing time is 1-8 h.
8. The method for preparing a sodium vanadium fluorophosphate-coated cathode material according to claim 7, wherein the mass of the cathode material in the step (2) is 13 times that of the vanadium element.
9. The method for producing a sodium vanadium fluorophosphate-coated cathode material according to claim 7, wherein the transition metal oxide in the step (2) is NanMnO2，0<n≤1；
And/or the polyanion compound is a NASICON-type polyanion compound, an olivine-type polyanion compound, a phosphate-based polyanion compound, a fluorophosphate-based polyanion compound, or a pyrophosphate-based polyanion compound;
and/or, in the molecular formula of the Prussian blue analogue, M is Fe, Co, Ni, Mn or Zn;
and/or the organic electrode material is poly 2,2,6, 6-tetramethyl piperidinyloxy-4-vinyl ether.
10. The method for preparing a vanadium sodium fluorophosphate-coated cathode material according to claim 9, wherein the prussian blue analogue is Na2MnFe(CN)6。
11. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 7, wherein the stirring speed in the step (2) is 200-300 rpm;
and/or the mixing time is 0.5-2 h;
and/or the mixing temperature is 50-70 ℃.
12. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 11, wherein the mixing time in the step (2) is 1-1.5 h;
and/or the temperature of the mixing is 60 ℃.
13. The method for producing a sodium vanadium fluorophosphate-coated cathode material according to claim 7, wherein the dispersion in the step (2) is performed under ultrasound;
and/or the power of the ultrasonic wave is 200-600W;
and/or the ultrasonic time is 10-40 min;
and/or the mass volume ratio of the cathode material to water is 5-20 mg/mL.
14. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 13, wherein the power of the ultrasound in the step (2) is 400-500W;
and/or the ultrasonic time is 20-30 min;
and/or the mass-volume ratio of the cathode material to water is 10 mg/mL.
15. The method for preparing the sodium vanadium fluorophosphate-coated cathode material according to claim 7, wherein the standing time in the step (2) is 3-6 h.
16. The method of preparing a sodium vanadium fluorophosphate-coated cathode material according to claim 1, further comprising separating and drying.
17. The method of preparing a sodium vanadium fluorophosphate-coated cathode material according to claim 16, wherein the separation is centrifugation.
18. The method for preparing a sodium vanadium fluorophosphate-coated cathode material according to claim 16, wherein the drying is performed under vacuum or a protective atmosphere;
and/or the drying temperature is 100-200 ℃;
and/or the drying time is 6-18 h.
19. The method for preparing a sodium vanadium fluorophosphate-coated cathode material according to claim 18, wherein the protective atmosphere is a nitrogen or argon atmosphere;
and/or the drying time is 12 h.
20. The sodium vanadium fluorophosphate-coated cathode material prepared by the preparation method of the sodium vanadium fluorophosphate-coated cathode material according to any one of claims 1 to 19.
21. The sodium vanadium fluorophosphate-coated cathode material according to claim 20, which comprises a cathode material and a sodium vanadium fluorophosphate coating layer, wherein the sodium vanadium fluorophosphate coating layer is uniformly coated on the surface of the cathode material; the molecular formula of the sodium vanadium fluorophosphate is Na3(VO1−xPO4)2F1+2xWherein x is more than or equal to 0 and less than or equal to 1.
22. The sodium vanadium fluorophosphate-coated cathode material according to claim 21, wherein the thickness of the sodium vanadium fluorophosphate-coated layer is 5nm or more.
23. The sodium vanadium fluorophosphate-coated cathode material according to claim 21, wherein the thickness of the sodium vanadium fluorophosphate-coated layer is 10 to 50 nm.
24. The sodium vanadium fluorophosphate-coated cathode material according to claim 21, wherein the thickness of the sodium vanadium fluorophosphate-coated layer is 30 nm.
25. A sodium-ion battery, wherein the positive electrode material is the vanadium sodium fluorophosphate-coated positive electrode material according to any one of claims 20 to 24.
26. Use of the sodium vanadium fluorophosphate-coated cathode material according to any one of claims 20 to 24 in a sodium-ion battery.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306771A (en) * | 2011-08-17 | 2012-01-04 | 中南大学 | Preparation method of vanadium sodium fluophosphate cathode material of hybrid ion battery |
| JP2013089391A (en) * | 2011-10-14 | 2013-05-13 | Kyushu Univ | Electrode active material for sodium ion secondary battery |
| CN105098177A (en) * | 2014-04-24 | 2015-11-25 | 宁德时代新能源科技有限公司 | Secondary lithium battery and positive electrode material thereof, and positive electrode material preparation method |
| CN105206831A (en) * | 2015-08-05 | 2015-12-30 | 北京工业大学 | Preparation method for sodium-ion battery cathode material Na3V2O2x(PO4)2F3-2x microspheres |
| CN105655565A (en) * | 2016-04-08 | 2016-06-08 | 苏州大学 | Composite cathode material of sodium-ion battery and preparation method of composite cathode material |
| CN106058212A (en) * | 2016-08-03 | 2016-10-26 | 苏州大学 | Composite cathode material of sodium-ion battery and preparation method of composite cathode material |
| CN106299248A (en) * | 2016-08-24 | 2017-01-04 | 东北师范大学 | A kind of fluorophosphate quadrangular nano material and preparation method thereof |
| CN106495124A (en) * | 2015-09-08 | 2017-03-15 | 中国科学院过程工程研究所 | A kind of fluorophosphoric acid vanadium sodium salt, low temperature environment-friendly preparation method thereof and application thereof |
| CN108808068A (en) * | 2018-05-10 | 2018-11-13 | 宁德时代新能源科技股份有限公司 | Secondary battery |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8835041B2 (en) * | 2011-01-14 | 2014-09-16 | Uchicago Argonne, Llc | Electrode materials for sodium batteries |
| US10833321B2 (en) * | 2015-03-06 | 2020-11-10 | Uchicago Argonne, Llc | Cathode materials for lithium ion batteries |
| KR102557725B1 (en) * | 2015-09-25 | 2023-07-24 | 삼성에스디아이 주식회사 | Composite anode active material, anode including the material, and lithium secondary battery including the anode |
| FR3042313B1 (en) * | 2015-10-13 | 2020-04-03 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | PROCESS FOR THE PREPARATION OF A PARTICULATE MATERIAL NA3V2 (PO4) 2F3 |
| CN107819115B (en) * | 2017-10-13 | 2020-09-11 | 北京科技大学 | Doped modified sodium vanadium fluorophosphate cathode material and preparation method thereof |
| TWI641177B (en) * | 2017-11-10 | 2018-11-11 | 中原大學 | Electrode material of sodium-ion battery, method of manufacturing the same and electrode of sodium-ion battery |
| US10637043B2 (en) * | 2017-11-30 | 2020-04-28 | Global Graphene Group, Inc. | Anode particulates or cathode particulates and alkali metal batteries containing same |
| CN108199028A (en) * | 2018-01-10 | 2018-06-22 | 中南大学 | A kind of NaVPO4F/C composite materials and preparation method thereof |
| CN108550814B (en) * | 2018-04-17 | 2020-06-12 | 中南大学 | Preparation method and application of modified sodium vanadium fluorophosphate cathode material |
-
2019
- 2019-07-10 CN CN201910621286.8A patent/CN112216823B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306771A (en) * | 2011-08-17 | 2012-01-04 | 中南大学 | Preparation method of vanadium sodium fluophosphate cathode material of hybrid ion battery |
| JP2013089391A (en) * | 2011-10-14 | 2013-05-13 | Kyushu Univ | Electrode active material for sodium ion secondary battery |
| CN105098177A (en) * | 2014-04-24 | 2015-11-25 | 宁德时代新能源科技有限公司 | Secondary lithium battery and positive electrode material thereof, and positive electrode material preparation method |
| CN105206831A (en) * | 2015-08-05 | 2015-12-30 | 北京工业大学 | Preparation method for sodium-ion battery cathode material Na3V2O2x(PO4)2F3-2x microspheres |
| CN106495124A (en) * | 2015-09-08 | 2017-03-15 | 中国科学院过程工程研究所 | A kind of fluorophosphoric acid vanadium sodium salt, low temperature environment-friendly preparation method thereof and application thereof |
| CN105655565A (en) * | 2016-04-08 | 2016-06-08 | 苏州大学 | Composite cathode material of sodium-ion battery and preparation method of composite cathode material |
| CN106058212A (en) * | 2016-08-03 | 2016-10-26 | 苏州大学 | Composite cathode material of sodium-ion battery and preparation method of composite cathode material |
| CN106299248A (en) * | 2016-08-24 | 2017-01-04 | 东北师范大学 | A kind of fluorophosphate quadrangular nano material and preparation method thereof |
| CN108808068A (en) * | 2018-05-10 | 2018-11-13 | 宁德时代新能源科技股份有限公司 | Secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| Supurior high-rate capability of Na3(VO0.5)2(PO4)2F2 nanoparticles embedded in porous graphene through the psedocapacitive effect;Xingde Xiang;《Chemical Communications》;20160201;全文 * |
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Effective date of registration: 20230418 Address after: 312000 2F, building B, Kechuang Park, No. 398, mahuan Road, Lihai street, Yuecheng District, Shaoxing City, Zhejiang Province Patentee after: Zhejiang sodium innovation energy Co.,Ltd. Address before: 200240 No. 800, Dongchuan Road, Shanghai, Minhang District Patentee before: SHANGHAI JIAO TONG University |