CN114604842A - Method for preparing nano sodium vanadium phosphate by nucleation, crystallization and isolation - Google Patents

Method for preparing nano sodium vanadium phosphate by nucleation, crystallization and isolation Download PDF

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CN114604842A
CN114604842A CN202210249477.8A CN202210249477A CN114604842A CN 114604842 A CN114604842 A CN 114604842A CN 202210249477 A CN202210249477 A CN 202210249477A CN 114604842 A CN114604842 A CN 114604842A
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phosphate
sodium
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CN114604842B (en
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张东彬
滕艾均
刘天豪
代宇
彭显著
尹翔鹭
曾泽华
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Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
Ansteel Beijing Research Institute
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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Abstract

The invention discloses a method for preparing nano vanadium sodium phosphate by nucleation, crystallization and isolation, which comprises the following steps: a. simultaneously inputting a vanadium source aqueous solution and an alkali source aqueous solution into a colloid mill to obtain hydroxyl vanadyl precursor slurry; b. dispersing the hydroxyl vanadyl precursor slurry prepared in the step a into a solvent, stirring and filtering to obtain a filter cake; c. and c, dispersing the filter cake obtained in the step b in a mixed aqueous solution of fluoride and phosphate, stirring, filtering and drying to obtain the sodium vanadium phosphate. The preparation method can effectively regulate and control the particle size of the vanadium sodium phosphate, realize the controllable preparation of the average particle size at the nanometer level, and the prepared vanadium sodium phosphate electrode material has good electrochemical performance and can be applied to electrode materials of lithium, sodium, potassium and other alkali metal secondary batteries.

Description

Method for preparing nano sodium vanadium phosphate by nucleation, crystallization and isolation
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a method for preparing nano sodium vanadium phosphate by nucleation, crystallization and isolation.
Background
The vanadium sodium phosphate has excellent sodium ion migration efficiency due to the special structural characteristics, and can be applied to the electrode materials of alkali metal ion secondary batteries such as sodium ions, lithium ions and the like. However, the poor electronic conductivity greatly limits the electrochemical performance of the vanadium sodium phosphate electrode material. In order to solve this problem, the following methods are mainly used: 1) the vanadium sodium phosphate/carbon composite material is prepared by introducing a substance having high electron conductivity, such as a carbon material. However, since the density of the carbon material is low, the introduction of the carbon material tends to cause a decrease in the tap and compacted density of the electrode material, which is disadvantageous for the study of a high loading amount of the electrode material. 2) The microscopic electronic structure of the sodium vanadium phosphate is regulated and controlled by doping and modifying anions and cations, and the intrinsic electronic conductivity of the material is improved. For example, by introducing high electronegative F anions, the microscopic charge distribution state of the sodium vanadium phosphate is changed, and the electron/ion conductivity of the sodium vanadium phosphate is improved. However, although the ion doping method has some effect in the laboratory research stage, how the effect after the quantification is still to be studied further. Therefore, further research on the preparation of sodium vanadium phosphate is necessary.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: by reducing the particle size of the sodium vanadium phosphate, the problem of slow electron transmission rate in the sodium vanadium phosphate can be effectively solved, so that the sodium vanadium phosphate has good electron conductivity, in other words, the sodium vanadium phosphate is subjected to nano design and preparation, the electron/ion transport efficiency of the sodium vanadium phosphate is favorably improved, and the sodium storage performance of the sodium vanadium phosphate is improved.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a method for preparing nano sodium vanadium phosphate by nucleation and crystallization isolation, the characteristics of high centrifugal force and high shear force of a colloid mill are utilized to quickly nucleate, and the organic/inorganic solvent environment is utilized to perform restrictive growth and transformation, so that the effective regulation and control of the particle size distribution of a sodium vanadium phosphate product are achieved, the nano preparation is realized, and the preparation method has the advantages of simple operation, high efficiency, easy industrial amplification and the like, and is beneficial to promoting the research and popularization and application of a sodium vanadium phosphate material in the field of electrochemical energy storage.
The method for preparing the nano vanadium sodium phosphate by nucleation, crystallization and isolation comprises the following steps:
a. simultaneously inputting a vanadium source aqueous solution and an alkali source aqueous solution into a colloid mill to obtain hydroxyl vanadyl precursor slurry;
b. dispersing the hydroxyl vanadyl precursor slurry prepared in the step a into a solvent, stirring and filtering to obtain a hydroxyl vanadyl precursor filter cake;
c. and c, dispersing the hydroxyl vanadyl precursor filter cake obtained in the step b into a mixed aqueous solution of fluoride and phosphate, stirring, filtering and drying to obtain the sodium vanadium phosphate.
The method for preparing the nano vanadium sodium phosphate by the nucleation, crystallization and isolation of the embodiment of the invention brings advantages and technical effects, 1, the method of the embodiment of the invention adopts the nucleation, crystallization and isolation method to prepare the nano vanadium sodium phosphate, and by utilizing the characteristics of high centrifugal force and high shearing force of a colloid mill, the solution rotates at a high speed in a liquid film of 5-20 mu, the mass transfer resistance is reduced to the lowest value, the collision probability is greatly improved, and then a plurality of tiny nano crystal nuclei are rapidly formed, so that the rapid nucleation of hydroxyl vanadyl precursor is realized; 2. the method of the embodiment of the invention changes the condition of a crystal nucleus crystallization growth system, disperses hydroxyl vanadyl precursor slurry formed after colloid milling treatment in an organic/inorganic solvent, regulates and controls the interaction of water molecules in the solution, utilizes the principle of different polarities of the solvent, changes the hydration action force of the hydroxyl vanadyl precursor slurry by changing the solvent system of the hydroxyl vanadyl, ensures that the crystal nucleus is not easy to contact with the crystal nucleus, and controls the further growth between the crystal nucleus and the crystal nucleus, thereby achieving the purpose of controlling the grain size of the material and realizing the control of crystallization growth; 3. in the method of the embodiment of the invention, a hydroxyl vanadyl precursor filter cake obtained by filtering after dispersing in a solvent is placed in a mixed aqueous solution of fluoride and phosphate, and the preparation of sodium vanadium phosphate is realized by an in-situ ion exchange technology; 4. the method of the embodiment of the invention can effectively regulate and control the particle size of the vanadium sodium phosphate particles, and realize controllable preparation of the average particle size at nanometer level; 5. the vanadium sodium phosphate material prepared by the method of the embodiment of the invention has good conductivity, good wettability in electrolyte, good electron/ion transport efficiency and excellent electrochemical performance, and is suitable for being used as an electrode material of lithium, sodium, potassium and other alkali metal secondary batteries; 6. the method provided by the embodiment of the invention has the advantages of simple and convenient preparation conditions, easiness in scale-up production and wide application prospect in electrode materials of lithium, sodium, potassium and other alkali metal secondary batteries.
In some embodiments, in step a, the source of vanadium is a source of trivalent or tetravalent vanadium, or alternatively, the source of vanadium is a mixture of a source of pentavalent vanadium and a reducing agent; the alkali source comprises at least one of sodium hydroxide, potassium hydroxide and ammonia water; the concentration of the vanadium source water solution is 0.1-5.0 mol/L, and the concentration of the alkali source water solution is 0.5-5.0 mol/L.
In some embodiments, in step a, the trivalent or tetravalent vanadium source comprises at least one of vanadyl sulfate, vanadyl oxalate, vanadium chloride, vanadium battery electrolyte, and the mixture of pentavalent vanadium source and reducing agent comprises at least one of a mixture of vanadium pentoxide and oxalic acid or a mixture of sodium metavanadate and hydroxylamines.
In some embodiments, the colloid mill is provided with a circulation tube for the vanadyl precursor slurry exiting the hopper to return to the hopper.
In some embodiments, in step a, the ratio of the feeding rate of the vanadium source aqueous solution to the feeding rate of the alkali source aqueous solution into the colloid mill is 1: 1-5: 1, the rotation speed of the colloid mill is 500-3000 rpm, and the back mixing time is 0-10 min.
In some embodiments, in step b, the solvent comprises at least one of an inorganic solvent or an organic solvent.
In some embodiments, in step b, the organic solvent includes at least one of alcohol, ketone, and ether, and the inorganic solvent is deionized water.
In some embodiments, in step c, the fluoride comprises at least one of sodium fluoride, potassium fluoride, ammonium fluoride; the phosphate comprises at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate and sodium phosphate; the molar concentration ratio of the fluoride to the phosphate is 0-1: 10.
In some embodiments, the molar ratio of the vanadium source to the phosphate is from 1:1 to 1: 3.
In some embodiments, in step b, the stirring time is 1-24 h; in the step c, the stirring time is 6-24 h.
Drawings
FIG. 1 is an XRD plot of sodium vanadium phosphate prepared by the method of example 1;
FIG. 2 is an SEM characterization of sodium vanadium phosphate prepared by the method of example 1;
FIG. 3 is a particle size distribution test of a sodium vanadium phosphate material prepared by the method of example 1;
FIG. 4 is a particle size distribution test of the sodium vanadium phosphate material prepared by the method of example 2;
FIG. 5 is a constant current charge and discharge curve of the sodium vanadium phosphate material prepared by the method of example 3;
FIG. 6 is a particle size distribution test of a sodium vanadium phosphate material prepared by the method of example 6;
FIG. 7 is a particle size distribution test of a sodium vanadium phosphate material prepared by the method of comparative example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The method for preparing the nano vanadium sodium phosphate by nucleation, crystallization and isolation comprises the following steps:
a. simultaneously inputting a vanadium source aqueous solution and an alkali source aqueous solution into a colloid mill to obtain hydroxyl vanadyl precursor slurry;
b. dispersing the hydroxyl vanadyl precursor slurry prepared in the step a into a solvent, stirring and filtering to obtain a hydroxyl vanadyl precursor filter cake;
c. and c, dispersing the hydroxyl vanadyl precursor filter cake obtained in the step b into a mixed aqueous solution of fluoride and phosphate, stirring, filtering and drying to obtain the sodium vanadium phosphate.
According to the method for preparing nano vanadium sodium phosphate by nucleation, crystallization and isolation, the nano vanadium sodium phosphate is prepared by adopting a nucleation, crystallization and isolation method, and by utilizing the characteristics of high centrifugal force and high shearing force of a colloid mill, a solution rotates at a high speed in a liquid film of 5-20 mu, the mass transfer resistance is reduced to the lowest value, the collision probability is greatly improved, and then a plurality of tiny nano crystal nuclei are quickly formed, so that the quick nucleation of a hydroxyl vanadyl precursor is realized; the method of the embodiment of the invention changes the condition of a crystal nucleus crystallization growth system, disperses hydroxyl vanadyl precursor slurry formed after colloid milling treatment in an organic/inorganic solvent, regulates and controls the interaction of water molecules in the solution, utilizes the principle of different polarities of the solvent, changes the hydration action force of the hydroxyl vanadyl precursor slurry by changing the solvent system of the hydroxyl vanadyl, ensures that the crystal nucleus is not easy to contact with the crystal nucleus, and controls the further growth between the crystal nucleus and the crystal nucleus, thereby achieving the purpose of controlling the grain size of the material and realizing the control of crystallization growth; in the method of the embodiment of the invention, a hydroxyl vanadyl precursor filter cake obtained by filtering after dispersing in a solvent is placed in a mixed aqueous solution of fluoride and phosphate, and the preparation of sodium vanadium phosphate is realized by an in-situ ion exchange technology; the method of the embodiment of the invention can effectively regulate and control the particle size of the vanadium sodium phosphate particles, and realize controllable preparation of the average particle size at nanometer level; the vanadium sodium phosphate material prepared by the method of the embodiment of the invention has good conductivity, good wettability in electrolyte, good electron/ion transport efficiency and excellent electrochemical performance, and is suitable for being used as an electrode material of lithium, sodium, potassium and other alkali metal secondary batteries; the method provided by the embodiment of the invention has the advantages of simple and convenient preparation conditions, easiness in scale-up production and wide application prospect in electrode materials of lithium, sodium, potassium and other alkali metal secondary batteries.
In some embodiments, in step a, the vanadium source is a trivalent or tetravalent vanadium source, preferably including at least one of vanadyl sulfate, vanadyl oxalate, vanadium chloride, vanadium battery electrolyte; or the vanadium source is a mixture of a pentavalent vanadium source and a reducing agent, and preferably at least one of a mixture of vanadium pentoxide and oxalic acid or a mixture of sodium metavanadate and hydroxylamines is included; the alkali source comprises at least one of sodium hydroxide, potassium hydroxide and ammonia water. More preferably, the concentration of the vanadium source aqueous solution is 0.1-5.0 mol/L, and the concentration of the alkali source aqueous solution is 0.5-5.0 mol/L.
In some embodiments, the colloid mill is provided with a circulation pipe for the vanadyl oxyhydroxide slurry leaving the hopper to return to the hopper. In the embodiment of the invention, the colloid mill provided with the circulating pipe is preferably adopted, so that the slurry after the collision mixing in the hopper leaves the hopper can be returned to the hopper through the circulating pipe for collision mixing again, the collision times among materials are increased, the increase of the nucleation amount is facilitated, and the yield is improved.
In some embodiments, in step a, the ratio of the feeding rate of the vanadium source aqueous solution to the feeding rate of the alkali source aqueous solution into the colloid mill is 1: 1-5: 1, the rotation speed of the colloid mill is 500-3000 rpm, preferably 2000-3000 rpm, and the back mixing time is 0-10 min. In the method of the embodiment of the invention, the ratio of the speed of injecting the vanadium source aqueous solution and the alkali source aqueous solution into the colloid mill is preferably 1: 1-2: 1, too small ratio of the speed can cause too strong alkalinity, the product is impure, too large ratio of the speed can cause too little nucleation, and the speed is relatively slow; the rotating speed of the colloid mill greatly influences the size of crystal nuclei, the larger the rotating speed is, the smaller the crystal nuclei are generally, but the higher the energy consumption is, the crystal nuclei can be enlarged by too slow rotating speed. In the embodiment of the invention, the back mixing refers to that the precursor slurry formed by collision after entering the hopper in the colloid mill returns to the hopper again after leaving the hopper. Proper back-mixing increases the collision probability of the solution and promotes rapid nucleation, but if the back-mixing time is too long, partial crystallization of crystal nuclei may occur, resulting in large particle size.
In some embodiments, in step b, the solvent comprises at least one of an inorganic solvent or an organic solvent; preferably, the organic solvent includes at least one of alcohol such as ethanol and acetone, ketone and ether, and the inorganic solvent is deionized water. In the embodiment of the invention, the solvent is not particularly limited, and the hydroxyl vanadyl precursor slurry is dispersed by the solvent, so that the combined growth and transformation between the crystal nucleus and the crystal nucleus can be controlled, and the aim of controlling the particle size of the material is fulfilled.
In some embodiments, in step c, the fluoride comprises at least one of sodium fluoride, potassium fluoride, ammonium fluoride; the phosphate comprises at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate and sodium phosphate; the molar concentration ratio of the fluoride to the phosphate is 0-1: 10. In the method of the embodiment of the invention, the preparation of the sodium vanadium phosphate is realized by an in-situ ion exchange technology, preferably, fluoride can be added to be used as a fluorine source, and the performance of the sodium vanadium phosphate can be further improved by introducing F ions into the crystal structure of the sodium vanadium phosphate to dope and modify the sodium vanadium phosphate; the concentration ratio of fluoride to phosphate is further controlled, the doping amount of F element can be regulated, but F element is caused by excessive addition of fluoride-And PO4 3-Competing exchanges during ion exchange affect product purity.
In some embodiments, the molar concentration ratio of the vanadium source to the phosphate is 1:1 to 1: 3. In the method of the embodiment of the invention, the molar ratio of the vanadium source to the phosphate is further optimized, which is beneficial to improving the conversion rate of the vanadium source.
In some embodiments, in step b, the stirring time is 1-24 h; in the step c, the stirring time is 6-24 h. In the examples of the present invention, the stirring time in step b and step c is not particularly limited, and sufficient dispersion and reaction can be achieved.
In the examples of the invention, the vanadium sodium phosphate is prepared and its chemistryFormula is NaVOPO4Or Na3(VOPO4)2F or Na3(VPO4)2F3Or Na3V2(PO4)3The microscopic morphology of the nano-particle is nano-particle, the nano-particle size distribution of the particles is concentrated, and the nano-particle has a higher specific surface area.
The present invention is described in detail below with reference to examples and the accompanying drawings.
Example 1
13.6g of vanadyl sulfate is weighed and dissolved in 100mL of deionized water to prepare a vanadium source aqueous solution A. 10.6g of sodium hydroxide was weighed and dissolved in 100mL of deionized water to prepare an alkali source aqueous solution B.
And simultaneously inputting the solution A and the solution B into a colloid mill at the flow rate of 30mL/min, and adjusting the rotation speed of the colloid mill to 2000rpm and the back mixing time to be 3min to obtain precursor slurry.
Dispersing the prepared precursor slurry in an ethanol solvent, stirring for 3h, and filtering to obtain a precursor filter cake.
The obtained filter cake was dispersed in 100mL of a mixed solution C of 2.4g of sodium fluoride and 18.0g of sodium dihydrogenphosphate, stirred for 24 hours, filtered and dried to obtain sodium vanadium phosphate.
The XRD curve of the sodium vanadium phosphate prepared by the embodiment of the invention is shown in figure 1, and as can be seen from figure 1, the characteristic diffraction peaks of the curve at 16.3 degrees, 27.9 degrees, 32.6 degrees, 43.4 degrees and 44.6 degrees respectively correspond to Na3(VOPO4)2The (002), (200), (202), (301) and (105) crystal faces of F show that the obtained sample product has better crystallinity.
As can be seen from FIG. 2, the micro-morphology of the sodium vanadium phosphate prepared by the embodiment of the invention is nano-granular.
As can be seen from FIG. 3, the particle size distribution of the sodium vanadium phosphate nanoparticles prepared by the embodiment of the present invention is relatively concentrated, and is mainly distributed around 100 nm.
Electrochemical tests are carried out on the vanadium sodium phosphate prepared by the embodiment of the invention, the specific capacity of the prepared vanadium sodium phosphate is 105mAh/g under the condition of 50mA/g of charge-discharge current density, and the vanadium sodium phosphate can be applied to sodium ion secondary battery electrode materials.
Example 2
11.7g of ammonium metavanadate and 19.7g of hydroxylamine phosphate were weighed and dissolved in 100mL of deionized water to prepare a vanadium source aqueous solution A. 20.0g of sodium hydroxide was weighed and dissolved in 100mL of deionized water to prepare an alkali source aqueous solution B.
And simultaneously inputting the solution A and the solution B into a colloid mill at the flow rate of 50mL/min, and adjusting the rotation speed of the colloid mill to be 2500rpm and the back mixing time to be 1min to obtain precursor slurry.
And dispersing the prepared precursor slurry in a deionized water solvent, stirring for 3h, and filtering to obtain a precursor filter cake.
The obtained filter cake was dispersed in 100mL of a mixed solution C of 4.8g of sodium fluoride and 24.0g of sodium dihydrogenphosphate, stirred for 24 hours, filtered and dried to obtain sodium vanadium phosphate.
As can be seen from FIG. 4, the average particle size distribution of the sodium vanadium phosphate prepared in this example is relatively concentrated, mainly around 200 nm.
Electrochemical tests are carried out on the vanadium sodium phosphate prepared by the embodiment of the invention, the specific capacity of the prepared vanadium sodium phosphate is 98mAh/g under the condition of 50mA/g of charge-discharge current density, and the vanadium sodium phosphate can be applied to sodium ion secondary battery electrode materials.
Example 3
15.3g of vanadium chloride is weighed and dissolved in 100mL of deionized water to prepare a vanadium source aqueous solution A. 100mL of 3mol/L ammonia water solution was weighed as the alkali source aqueous solution B.
And (3) simultaneously inputting the solution A and the solution B into a colloid mill at the flow rate of 80mL/min, adjusting the rotation speed of the colloid mill to be 2500rpm, and setting the back mixing time to be 0 to obtain precursor slurry.
Dispersing the prepared precursor slurry into a mixed solvent of ethanol and deionized water with the volume ratio of 1:1, stirring for 24h, and filtering to obtain a precursor filter cake.
The obtained filter cake is dispersed into 100mL of 24.0g sodium dihydrogen phosphate solution C, stirred for 12h, filtered and dried to obtain the sodium vanadium phosphate.
The average particle size of the sodium vanadium phosphate prepared in this example was about 90 nm.
By performing an electrochemical test on the sodium vanadium phosphate prepared in the embodiment of the invention, as can be seen from fig. 5, under the condition of a charge-discharge current density of 50mA/g, the specific capacity of the sodium vanadium phosphate prepared in the embodiment is 106mAh/g, and the sodium vanadium phosphate can be applied to an electrode material of a sodium ion secondary battery.
Example 4
The same procedure as in example 1 was followed, except that the rotational speed of the colloid mill was 1000 rpm.
The particle size of the sodium vanadium phosphate obtained in example 4 was about 200 nm.
The specific capacity of the sodium vanadium phosphate prepared in the example 4 is 93mAh/g under the condition of 50mA/g of charge-discharge current density.
Example 5
The same procedure as in example 1 was followed, except that the rotational speed of the colloid mill was 500 rpm.
The particle size of the sodium vanadium phosphate obtained in example 5 was about 300 nm.
The specific capacity of the sodium vanadium phosphate prepared in the example 5 is 81mAh/g under the condition of 50mA/g of charge-discharge current density.
Example 6
The same procedure as in example 1 was followed, except that the rotational speed of the colloid mill was 3000 rpm.
As shown in FIG. 6, the particle size of the sodium vanadium phosphate obtained in example 6 was about 80 nm.
The specific capacity of the sodium vanadium phosphate prepared in the example 6 is 109mAh/g under the condition of 50mA/g of charge-discharge current density.
Example 7
The same procedure as in example 1 was repeated, except that the vanadium source aqueous solution A was fed to the colloid mill at a flow rate of 120mL/min and the alkali source aqueous solution B at a flow rate of 30 mL/min.
The particle size of the sodium vanadium phosphate obtained in example 7 was about 300 nm.
The specific capacity of the sodium vanadium phosphate prepared in example 7 was 77mAh/g under the condition of a charge-discharge current density of 50 mA/g.
Example 8
The same procedure as in example 1, except that the back-mixing time was 10 min.
The particle size of the sodium vanadium phosphate obtained in example 8 was about 300 nm.
The specific capacity of the sodium vanadium phosphate prepared in the example 8 is 75mAh/g under the condition of 50mA/g of charge-discharge current density.
Comparative example 1
The process was the same as in example 1, except that the solvent dispersion step was omitted and the precursor slurry obtained after colloid milling was directly dispersed in a mixed solution of sodium fluoride and sodium dihydrogen phosphate to obtain sodium vanadium phosphate.
As shown in FIG. 7, the particle size of the sodium vanadium phosphate prepared in comparative example 1 was about 300 nm.
The specific capacity of the sodium vanadium phosphate prepared in the comparative example 1 is 71mAh/g under the condition of 50mA/g of charge-discharge current density.
Comparative example 2
The same as the method of example 1, except that the vanadium source aqueous solution a and the alkali source aqueous solution B were directly mixed without colloid mill treatment, and stirred uniformly at a stirring speed of 500rmp to obtain a precursor slurry.
The particle size of the sodium vanadium phosphate prepared in comparative example 2 is about 350 nm.
The specific capacity of the sodium vanadium phosphate prepared in the comparative example 2 is 69mAh/g under the condition of 50mA/g of charge-discharge current density.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A method for preparing nano sodium vanadium phosphate by nucleation, crystallization and isolation is characterized by comprising the following steps:
a. simultaneously inputting a vanadium source aqueous solution and an alkali source aqueous solution into a colloid mill to obtain hydroxyl vanadyl precursor slurry;
b. dispersing the hydroxyl vanadyl precursor slurry prepared in the step a into a solvent, stirring and filtering to obtain a filter cake;
c. and c, dispersing the filter cake obtained in the step b in a mixed aqueous solution of fluoride and phosphate, stirring, filtering and drying to obtain the sodium vanadium phosphate.
2. The nucleation crystallization isolation preparation method for nano sodium vanadium phosphate according to claim 1, wherein in the step a, the vanadium source is trivalent or tetravalent vanadium source, or the vanadium source is a mixture of pentavalent vanadium source and reducing agent; the alkali source comprises at least one of sodium hydroxide, potassium hydroxide and ammonia water; the concentration of the vanadium source water solution is 0.1-5.0 mol/L, and the concentration of the alkali source water solution is 0.5-5.0 mol/L.
3. The nucleation and crystallization isolation preparation method for nano sodium vanadium phosphate according to claim 2, wherein in the step a, the trivalent or tetravalent vanadium source comprises at least one of vanadyl sulfate, vanadyl oxalate, vanadium chloride and vanadium battery electrolyte, and the mixture of the pentavalent vanadium source and the reducing agent comprises at least one of a mixture of vanadium pentoxide and oxalic acid or a mixture of sodium metavanadate and hydroxylamine.
4. The nucleation crystallization isolation preparation method for nano sodium vanadium phosphate according to claim 1, wherein the colloid mill is provided with a circulation pipe for the hydroxyl vanadyl precursor slurry leaving the hopper to return to the hopper.
5. The method for preparing nano sodium vanadium phosphate through nucleation, crystallization and isolation according to claim 1 or 4, wherein in the step a, the ratio of the infusion rate of the vanadium source aqueous solution and the infusion rate of the alkali source aqueous solution into the colloid mill is 1: 1-5: 1, the rotation speed of the colloid mill is 500-3000 rpm, and the back mixing time is 0-10 min.
6. The nucleation and crystallization isolation method for preparing nano sodium vanadium phosphate according to claim 1, wherein in the step b, the solvent comprises at least one of an inorganic solvent or an organic solvent.
7. The nucleation and crystallization isolation method for preparing nano sodium vanadium phosphate according to claim 6, wherein in the step b, the organic solvent comprises at least one of alcohol, ketone and ether, and the inorganic solvent is deionized water.
8. The nucleation and crystallization isolation method for preparing nano sodium vanadium phosphate according to claim 1, wherein in the step c, the fluoride comprises at least one of sodium fluoride, potassium fluoride and ammonium fluoride; the phosphate comprises at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate and sodium phosphate; the molar concentration ratio of the fluoride to the phosphate is 0-1: 10.
9. The nucleation crystallization isolation preparation method for nano sodium vanadium phosphate according to claim 1 or 8, wherein the molar concentration ratio of the vanadium source to the phosphate is 1: 1-1: 3.
10. The nucleation crystallization isolation preparation method for nano sodium vanadium phosphate according to claim 1, wherein in the step b, the stirring time is 1-24 h; in the step c, the stirring time is 6-24 h.
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CN1867514A (en) * 2003-11-14 2006-11-22 苏德-化学股份公司 Lithium metal phosphates, method for producing the same and use thereof as electrode material
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
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