CN111994889B - Positive electrode material of sodium vanadium phosphate sodium ion battery and preparation method thereof - Google Patents
Positive electrode material of sodium vanadium phosphate sodium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a vanadium sodium phosphate ion battery anode material and a preparation method thereof. And after the pole piece is coated by the vanadium sodium phosphate composite material powder, the sodium ion battery is assembled. In the step of preparing the NASICON sodium vanadium phosphate, raw materials are fully mixed through ball milling, so that particles are refined while being uniformly mixed, the original refined particle morphology is kept good through hydrothermal reaction and is completely reacted, and the material is obtained through solid phase sintering by one-step sintering, has excellent morphology, is fully reacted and has an optimized structure. The sodium vanadium phosphate electrode has high capacity, has initial specific capacity of up to 107.4 mA h/g under the current density of 100mA/g, is close to theoretical specific capacity and good in cycling stability, and the capacity is still kept to be equivalent to the initial state after 100 times of cycling charge and discharge.
Description
Technical Field
The invention belongs to the field of preparation of sodium ion battery electrode materials, and particularly relates to modification of a sodium vanadium phosphate sodium ion battery anode material and a preparation method thereof.
Background
At the beginning of the 21 st century, energy crisis and environmental pollution are becoming increasingly serious problems for us, and new rechargeable battery elements are becoming the development and application of new energy fields, among which sodium ion batteries are the earliest. The shortage of lithium resources has led to sodium ion batteries as an important point for future development. The sodium element has abundant reserves and relatively economical cost, and the sodium ion battery and the lithium ion battery have similar working principles, so the sodium ion battery has strong potential in filling the functions and the shortages of the lithium ion battery.
In sodium ion batteries, the positive electrode material is a key factor affecting the performance and cost of the battery, wherein NASICON-type sodium vanadium phosphate has a profound potential due to its excellent stability and relatively high specific capacity, however, sodium vanadium phosphate directly obtained by a chemical synthesis method is generally complex and cumbersome, low in yield and poor in performance. The spray drying method is adopted by the university of Chinese, cao Yuliang and the like, so that the conductivity of the sodium vanadium phosphate is improved, and the reversible specific capacity is up to 115mA h/g under the current density of 20 mA/g. Although this method achieves a substantial improvement in the conductivity of the material, the lower yield and the complexity of operation have led to the development of this method. The method for preparing the sodium vanadium phosphate by adopting the ball milling and solid phase sintering method is adopted by the university of Wuhan Jian Zelang and the like, so that the preparation efficiency is improved, the operation process is simplified, and the operation is simple and convenient and the repeatability is high. However, the method does not completely improve the problem of low conductivity of the sodium vanadium phosphate material, and the specific capacity can only reach 98.6mA h/g under the extremely small current density of 5 mA/g, and still has great improvement space. Recently, university of temporary Yi Jiang Xiaolei et al adopts a sol-gel method, and uses special beta-cyclodextrin as a carbon source to prepare a vanadium sodium phosphate composite material, wherein the material has excellent performance under the current density of 20mA/g and is stable in circulation under larger current. The experiment can not effectively realize the mass production and preparation of the material, and has a great improvement space for practical production and application.
Therefore, how to effectively and simply operate, and high-level preparation of NASICON type sodium vanadium phosphate with stable performance becomes one of key problems in the related technology of sodium ion batteries.
Disclosure of Invention
The invention aims to provide a vanadium sodium phosphate sodium ion battery anode material and a preparation method thereof, so that the capacity and the cycling stability of a sodium ion battery are improved.
In order to solve the above technical problems, according to one aspect of the present invention, there is provided a method for preparing a positive electrode material of a sodium vanadium phosphate ion battery, comprising:
uniformly mixing ammonium metavanadate, sodium dihydrogen phosphate dihydrate and glucose in proportion, then adding an ethanol solution, placing the obtained solution on a ball mill, stirring uniformly at the rotating speed of 600-2800 rpm to obtain sodium vanadium phosphate precursor slurry, placing the slurry in an oven, drying at 45-125 ℃ for 1-24 hours, and then placing in a vacuum oven for drying at the same temperature for 1-24 hours to obtain sodium vanadium phosphate precursor powder;
mixing the obtained vanadium phosphate precursor powder into deionized water, magnetically stirring, and transferring to a high-pressure hydrothermal reaction kettle for hydrothermal reaction, wherein the hydrothermal temperature is 150-220 ℃ and the reaction time is 8-72 h; then drying in a vacuum oven at 45-125 ℃ for 1-24 hours to obtain a sodium vanadium phosphate precursor;
transferring the sodium vanadium phosphate precursor into a solid-phase sintering furnace, heating to 250-400 ℃ at a heating rate of 1-10 ℃/min under the protection of mixed gas, sintering for 1-12 hours, and continuously heating to an annealing temperature of 600-1100 ℃ and sintering for 1-48 hours to obtain the NASICON sodium vanadium phosphate powder.
Further, in the first step, the molar ratio of the ammonium metavanadate, the sodium dihydrogen phosphate dihydrate and the glucose is 2:3:1.5.
Further, in the first step, the rotating speed of the ball mill is 1800rpm, and the ball milling time is 48 hours; the oven temperature was 80 ℃, dried for 4 hours, and vacuum dried at the same temperature for 12 hours.
Further, in the second step, the rotation speed of the magnetic stirrer was 600rpm, and the heating temperature was 75 ℃.
Further, in the third step, the temperature rising rate is 4 ℃/min, the sintering is carried out for 1 hour at the temperature of 350 ℃, and the sintering is carried out for 4 hours at the temperature of 750 ℃.
Further, in step three, ar/H 2 =95/5 (volume ratio) as a mixture gas.
According to another aspect of the invention, there is provided a vanadium sodium phosphate battery positive electrode material, which is obtained by the above preparation method.
According to another aspect of the present invention, there is provided a vanadium phosphate nano electrode sheet, which is prepared by dissolving 10-50 mL of PVDF in mg in 2 mL of NMP, adding 10-100 mg conductive carbon black and 10-300-mg sodium vanadium phosphate powder in accordance with claim 7 under magnetic stirring, stirring for 0.5-24 hours to obtain a mixed electrode slurry, coating the slurry on aluminum foil with a thickness of 0.3-0.9mm by an automatic coater, placing the coated aluminum foil in a vacuum oven, drying at 80-120 ℃ under an air pressure of-0.1 Mpa for 1-24 hours to obtain the vanadium phosphate nano electrode sheet.
Further, the slurry was obtained by stirring for 6 hours, the thickness of the coating film was 0.15. 0.15 mm, and the drying condition was 120 degrees centigrade and vacuum drying was performed for 12 hours.
According to one aspect of the invention, a sodium ion battery is provided, the vanadium sodium phosphate electrode plate is cut to obtain a wafer with the diameter of 12mm, the wafer is compacted by a tablet press, the compaction pressure is 10Mpa, then a sodium metal plate with the diameter of 12mm and the thickness of 0.2mm is used as a positive electrode, 0.1mL of 1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution is used as an electrolyte, and a polypropylene film with the diameter of 19mm is used as a diaphragm to assemble the button battery in a glove box filled with high-purity argon.
In the step of preparing the NASICON sodium vanadium phosphate, raw materials are fully mixed through ball milling, so that particles are refined while being uniformly mixed, the original refined particle morphology is kept good through hydrothermal reaction and is completely reacted, and the material is obtained through solid phase sintering by one-step sintering, has excellent morphology, is fully reacted and has an optimized structure.
The preparation method is simple, the raw materials are easy to obtain, the condition is mild, the energy consumption is extremely low, no byproducts are generated in the production process, and the used solvents and non-solvents are nontoxic or low in toxicity, so that the harm to human bodies is reduced. The main process of sample production can realize automation and unattended operation, and can realize mass production.
The NASICON type sodium vanadium phosphate obtained by the invention shows excellent capacity and circulation stability in a sodium ion battery, and in a better implementation mode, the initial specific capacity is as high as 107.4 mA h/g, and the specific capacity after 100 times of circulation is basically consistent with the initial capacity under the working current density of 100mA/g without obvious attenuation.
Drawings
FIG. 1 is a graph showing the first charge and discharge characteristics of the 750 ℃ sodium vanadium phosphate positive electrode material obtained in example 1 in a sodium ion battery;
FIG. 2 is a graph showing 100 cycles of the 750℃vanadium sodium phosphate positive electrode material obtained in example 1 in a sodium ion battery;
FIG. 3 is a graph showing the first charge and discharge characteristics of 850℃sodium vanadium phosphate positive electrode material obtained in example 2 in a sodium ion battery;
FIG. 4 is 100 cycle performance data of 850℃sodium vanadium phosphate positive electrode material obtained in example 2 in a sodium ion battery;
FIG. 5 is a graph showing the first charge and discharge characteristics of 950℃sodium vanadium phosphate positive electrode material obtained in example 3 in a sodium ion battery;
FIG. 6 is 100 cycle performance data of 950℃sodium vanadium phosphate positive electrode material obtained in example 3 in a sodium ion battery;
FIG. 7 is an SEM (scanning electron microscope) image of a 750 ℃ sodium vanadium phosphate positive electrode material obtained in example 1.
Detailed Description
The preparation method of the positive electrode material of the sodium vanadium phosphate ion battery provided by the typical embodiment of the invention comprises the following steps:
uniformly mixing ammonium metavanadate, sodium dihydrogen phosphate dihydrate and glucose in proportion, adding an ethanol solution, placing the obtained solution on a ball mill, stirring uniformly at the rotating speed of 600-2800 rpm to obtain sodium vanadium phosphate precursor slurry, placing the slurry in an oven, drying at 45-125 ℃ for 1-24 hours, and then placing in a vacuum oven for drying at the same temperature (45-125 ℃) for 1-24 hours to obtain sodium vanadium phosphate precursor powder.
In this step, preferably, the molar ratio of ammonium metavanadate, sodium dihydrogen phosphate dihydrate and glucose is 2:3:1.5. Ammonium metavanadate, sodium dihydrogen phosphate dihydrate, glucose in a molar ratio of 2:3:1.5 are added to a stainless steel ball milling tank, and 10-90 mL ethanol solution, preferably 30ml ethanol solution, is added.
The ball mill adopts a planetary ball mill, and vanadium phosphate nano precursor slurry is obtained after ball milling. Preferably, the rotation speed is 600-2800 rpm for ball milling for 1-48 hours. Preferably, the rotation speed of the ball mill is 1800rpm, and the ball milling time is 48 hours; the oven temperature was 80℃and dried for 4 hours, and the same temperature (80 ℃) was vacuum dried for 12 hours.
The ball milling ensures that the raw materials are mixed more uniformly, promotes the complete occurrence of related reactions, and refines the size and granularity of the materials. The experiment finds that: the material performance obtained is best when the rotation speed of the ball mill reaches 1800rpm, and can reach 107.4 mA h/g.
Mixing the obtained vanadium phosphate precursor powder into deionized water, magnetically stirring, and transferring to a high-pressure hydrothermal reaction kettle for hydrothermal reaction, wherein the hydrothermal temperature is 150-220 ℃ and the reaction time is 8-72 h; and then drying in a vacuum oven at 45-125 ℃ for 1-24 hours to obtain the vanadium sodium phosphate precursor.
In the step, preferably, during magnetic stirring, the rotating speed of the magnetic stirrer is 300-1000 rpm, the heating temperature is 45-90 ℃ and the time is 5-180 min; further preferably, the magnetic stirrer is rotated at 600rpm, the heating temperature is 75℃and the time is 30 minutes.
Preferably, the hydrothermal temperature is 200 ℃ and the time is 24 h. The vacuum oven temperature was 120℃and dried for 12 hours.
The hydrothermal reaction can fully maintain the excellent morphology of the raw materials, and simultaneously, the reaction is more fully and completely realized, so that the electrochemical performance of the material is greatly improved. The experiment finds that: when the rotation speed of the magnetic stirrer is 600rpm, the heating at 75 ℃ is the key for improving the material performance, and the performance can reach 107.4 mA h/g.
Transferring the sodium vanadium phosphate precursor into a solid-phase sintering furnace, heating to 250-400 ℃ at a heating rate of 1-10 ℃/min under the protection of mixed gas, and sintering for 1-12 hours, and continuously heating to an annealing temperature of 600-1100 ℃ to sinter for 1-48 hours to obtain NASICON sodium vanadium phosphate powder, namely the sodium vanadium phosphate sodium ion battery anode material (Na 3V2 (PO 4) 3/C).
In this step, preferably Ar/H 2 =95/5 (volume ratio) as a mixture gas. Preferably, the temperature rising rate is 4 ℃/min, the sintering is carried out for 1 hour at 350 ℃, and the sintering is carried out for 4 hours at the temperature rising to 750 DEG CWhen (1).
The solid phase sintering can ensure that the material maintains a good crystal structure, optimize the performance of the material and play an important role in playing the performance of the material. The experiment finds that: the heating rate is 4 ℃/min, sintering is carried out for 1 hour at 350 ℃, the heating to 750 ℃ is the optimal condition for preparing excellent materials, the specific capacity can be 107.4 mA h/g, the cycle is 100 circles, and the capacity retention rate is still as high as 94.2%.
Another exemplary embodiment of the present invention provides that the vanadium sodium phosphate ion positive electrode material (Na 3V2 (PO 4) 3/C) is obtained by the above-described preparation method.
The vanadium phosphate nano-powder is adopted to prepare the vanadium phosphate nano-electrode plate. Dissolving 10-50-mg PVDF in 2 mL NMP, adding 10-100 mg conductive carbon black and 10-300-mg sodium vanadium phosphate powder under magnetic stirring, stirring for 0.5-24 hours uniformly to obtain mixed electrode slurry, coating the slurry on aluminum foil according to the thickness of 0.3-0.9mm by an automatic coating machine, placing the aluminum foil in a vacuum oven, drying for 1-24 hours at 80-120 ℃ under the air pressure of-0.1 Mpa, and obtaining the sodium vanadium phosphate electrode plate.
Preferably, the mixed electrode slurry is obtained by stirring for 6 hours under magnetic stirring, the thickness of a coating film is 0.15 and mm, and the drying condition is 120 ℃ and vacuum drying is carried out for 12 hours.
The embodiment provides a sodium ion battery, which is formed by cutting the vanadium sodium phosphate electrode plate to obtain a wafer with the diameter of 12mm, compacting the wafer by a tablet press, wherein the compacting pressure is 10Mpa, then using the vanadium sodium phosphate wafer electrode plate as an anode, using a sodium metal plate with the diameter of 12mm and the thickness of 0.2mm as a cathode, using 0.1mL of 1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution as an electrolyte, and using a polypropylene film with the diameter of 19mm as a diaphragm to assemble the wafer in a glove box filled with high-purity argon.
The following examples are provided to further illustrate the claimed invention.
Example 1
Firstly, preparing vanadium sodium phosphate anode material
Firstly, weighing ammonium metavanadate (2.3396 g), sodium dihydrogen phosphate dihydrate (4.6803 g) and glucose (3.9634), adding into a stainless steel ball milling tank, adding 30mL ethanol solution, mixing, and carrying out ball milling at a speed of 1800rpm for 48 hours to obtain blue/bluish vanadium sodium phosphate precursor slurry, putting the blue/bluish vanadium sodium phosphate precursor slurry into an oven, drying at 80 ℃ for 2 hours, and drying at 80 ℃ for 14 hours in a vacuum oven to obtain bluish vanadium sodium phosphate precursor powder.
Weighing 5 g of the sodium vanadium phosphate precursor powder, placing in a 100 ml beaker, adding 70 ml deionized water, sealing a sealing film, placing on a magnetic stirrer, setting the rotating speed to be 600rpm and the temperature to be 75 ℃, fully stirring for 30 min, and taking out suspension liquid in a high-pressure hydrothermal reaction kettle. The hydrothermal temperature was set at 200℃for 24 h. Setting the vacuum oven at 120 ℃ after the reaction is finished and the time of the vacuum oven is 12 h to obtain the vanadium sodium phosphate precursor.
Step three, putting the vanadium sodium phosphate precursor into a tube furnace to obtain a mixed gas (Ar/H) 2 =95/5) as a reducing atmosphere, the heating rate is 4 ℃/min, the temperature is raised to 350 ℃ and the sintering is carried out for 1 hour, the same heating rate is continued to be raised to 750 ℃, and the sintering is carried out for 4 hours at constant temperature, thus obtaining black sodium vanadium phosphate powder.
(II) preparing vanadium sodium phosphate electrode plate
20 mg of PVDF is dissolved in 2 mL of NMP, 40 mg conductive carbon black and 140 mg sodium vanadium phosphate are slowly added with stirring, the slurry is coated on an aluminum foil by a coating machine according to the thickness of 0.1 mm after stirring for 6 hours, and then the aluminum foil is dried for 12 hours at 120 ℃ under vacuum, so that the sodium vanadium phosphate electrode plate is obtained.
(III) preparation of sodium ion Battery
Cutting a sodium vanadium phosphate electrode plate to obtain a wafer with the diameter of 12mm, compacting the wafer by a tablet press under the compaction pressure of 10Mpa, then taking the sodium metal plate with the diameter of 12mm and the thickness of 0.2mm as a cathode by taking the sodium metal plate with the diameter of 12mm as the cathode, taking 0.1mL of 1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution as electrolyte, taking a polypropylene film with the diameter of 19mm as a diaphragm, and assembling the polypropylene film in a glove box filled with high-purity argon to obtain the CR2016 button cell, and charging and discharging the cell on a cell test platform by using the current density of 100 mA/g.
Fig. 1 illustrates that at a solid phase sintering temperature of 750 ℃ (NVP/C-750), the resulting vanadium sodium phosphate composite material has a smooth voltage plateau and charge-discharge curve for a battery assembled as a positive electrode material of a sodium ion battery. The specific capacity can reach 107.4 mA h/g at the current density of 100mA/g, is extremely close to the theoretical specific capacity, and has extremely excellent conductive performance.
FIG. 2 illustrates that at a sintering temperature of 750℃the material is cycled 100 times at a current density of 100mA/g, with capacity retention still being as high as 94.2%, and cycle performance being excellent.
Example 2-example 7 differed from example 1 only in ball milling speed/time, step one drying temperature/time, magnetic stirring speed/temperature, solid phase sintering temperature/time, as shown in table 1. And performing performance test on the obtained button sodium ion battery to obtain corresponding charge and discharge data and cycle performance data, wherein the charge and discharge data and the cycle performance data correspond to the performance of the sodium ion battery made of the sodium vanadium phosphate material.
Table 1 the main parameters and sodium ion battery performance of examples 1-7
| Ball milling rotor Speed/time Interval (C) | Drying temperature- Time (step) One is that | Magnetic stirring Rotational speed/temperature Degree of | Shui Rewen Degree/time Interval (C) | Drying temperature- Time (step) Two is a third step of | Solid phase sintering Temperature/time Interval (C) | Current density 100mA/g, give Specific capacity of | |
| Real world Applying Example 1 | 1800rp m/48h | 80℃/16H | 600rpm/ 75℃ | 200℃/ 24H | 120℃/12H | 750℃/4H | 107.4 mA h/g |
| Real world Applying Example 2 | 1800rp m/48h | 80℃/16H | 600rpm/ 75℃ | 200℃/ 24H | 120℃/12H | 850℃/4H | 96.1 mA h/g |
| Real world Applying Example 3 | 1800rp m/48h | 80℃/16H | 600rpm/ 75℃ | 200℃/ 24H | 120℃/12H | 950℃/4H | 100.5 mA h/g |
| Real world Applying Example 4 | 1800rp m/48h | 80℃/16H | 700rpm/ 75℃ | 200℃/ 24H | 120℃/12H | 750℃/4H | 84.7 mA h/g |
| Real world Applying Example 5 | 1800rp m/48h | 80℃/16H | 800rpm/ 75℃ | 200℃/ 24H | 120℃/12H | 750℃/4H | 77.4 mA h/g |
| Real world Applying Example 6 | 1200rp m/48h | 80℃/16H | 600rpm/ 75℃ | 200℃/ 24H | 120℃/12H | 750℃/4H | 74.4 mA h/g |
| Real world Applying Example 7 | 1500rp m/48h | 80℃/16H | 600rpm/ 75℃ | 200℃/ 24H | 120℃/12H | 750℃/4H | 87.1 mA h/g |
For example 2, FIG. 3 illustrates that at a solid phase sintering temperature of 850 ℃ (NVP/C-850), the resulting sodium vanadium phosphate composite assembled sodium ion battery has a specific capacity of 96.1mA h/g at a current density of 100mA/g, and a conductivity lower than that of example 1. FIG. 4 illustrates that at a sintering temperature of 850℃the material is cycled 100 times at a current density of 100mA/g with a capacity retention of 85.4% and typical cycle performance.
For example 3, fig. 5 illustrates that at a solid phase sintering temperature of 950 ℃ (NVP/C-950), the resulting vanadium sodium phosphate composite assembled sodium ion battery can reach a specific capacity of 100.5 mA h/g at a current density of 100mA/g, with conductivity lower than example 1 but higher than example 2. FIG. 6 illustrates that at a sintering temperature of 950℃the material was cycled 100 times at a current density of 100mA/g with a capacity retention of 92.3% and cycling performance lower than example 1 but higher than example 2.
Example 8
Firstly, preparing vanadium sodium phosphate anode material
Firstly, weighing ammonium metavanadate (2.3396 g), sodium dihydrogen phosphate dihydrate (4.6803 g) and glucose (3.9634), adding 10mL of ethanol solution, mixing, and drying in a drying oven at 45 ℃ for 24 hours at the ball milling speed of 600rpm for 24 hours to obtain blue/bluish vanadium sodium phosphate precursor slurry, and drying in a vacuum drying oven at 45 ℃ for 24 hours to obtain bluish vanadium sodium phosphate precursor powder.
Weighing 5 g of the sodium vanadium phosphate precursor powder, placing in a 100 ml beaker, adding 70 ml deionized water, sealing a sealing film, placing on a magnetic stirrer, setting the rotating speed at 300 rpm and the temperature at 45 ℃, fully stirring for 180min, and taking out suspension liquid in a high-pressure hydrothermal reaction kettle. The hydrothermal temperature is set to 150 ℃ and the time is 72 hours. Setting the temperature of a vacuum oven at 45 ℃ and the time of 24 h after the reaction is finished, and obtaining the vanadium sodium phosphate precursor.
Step three, putting the vanadium sodium phosphate precursor into a tube furnace to obtain a mixed gas (Ar/H) 2 =95/5) as a reducing atmosphere, the heating rate is 1 ℃/min, the temperature is raised to 250 ℃ and the sintering is carried out for 12 hours, the same heating rate is continued to be raised to 600 ℃, and the sintering is carried out for 48 hours at constant temperature, thus obtaining black sodium vanadium phosphate powder.
(II) preparing vanadium sodium phosphate electrode plate
20 mg of PVDF is dissolved in 2 mL of NMP, 40 mg conductive carbon black and 140 mg sodium vanadium phosphate are slowly added with stirring, the slurry is coated on aluminum foil by a coating machine according to the thickness of 0.3 mm after stirring for 0.5 hours, and then the aluminum foil is dried for 24 hours at 80 ℃ under vacuum, so that the sodium vanadium phosphate electrode plate is obtained.
(III) preparation of sodium ion Battery
Cutting a sodium vanadium phosphate electrode plate to obtain a wafer with the diameter of 12mm, compacting the wafer by a tablet press under the compaction pressure of 10Mpa, then taking the sodium metal plate with the diameter of 12mm and the thickness of 0.2mm as a cathode by taking the sodium metal plate with the diameter of 12mm as the cathode, taking 0.1mL of 1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution as electrolyte, taking a polypropylene film with the diameter of 19mm as a diaphragm, and assembling the polypropylene film in a glove box filled with high-purity argon to obtain the CR2016 button cell, and charging and discharging the cell on a cell test platform by using the current density of 100 mA/g.
Example 9
Firstly, weighing ammonium metavanadate (2.3396 g), sodium dihydrogen phosphate dihydrate (4.6803 g) and glucose (3.9634), adding into a stainless steel ball milling tank, adding 90 mL ethanol solution, mixing, and carrying out ball milling at 2800rpm for 1 hour to obtain blue/bluish vanadium sodium phosphate precursor slurry, putting into an oven, drying at 125 ℃ for 1 hour, and drying at 125 ℃ for 1 hour in a vacuum oven to obtain bluish vanadium sodium phosphate precursor powder.
Weighing 5 g of the sodium vanadium phosphate precursor powder, placing in a 100 ml beaker, adding 70 ml deionized water, sealing a sealing film, placing on a magnetic stirrer, setting the rotating speed to 1000rpm and the temperature to 90 ℃, fully stirring for 5 min, and taking out suspension liquid in a high-pressure hydrothermal reaction kettle. The hydrothermal temperature was set at 220 ℃ for 8 h. Setting the vacuum oven at 125 ℃ after the reaction is finished and the time to be 1 h to obtain the vanadium sodium phosphate precursor.
Step three, putting the vanadium sodium phosphate precursor into a tube furnace to obtain a mixed gas (Ar/H) 2 =95/5) as a reducing atmosphere, the heating rate is 10 ℃/min, the temperature is raised to 400 ℃ and the sintering is carried out for 1 hour, the same heating rate is continued to be raised to 1100 ℃, and the sintering is carried out for 1 hour at constant temperature, so that the black sodium vanadium phosphate powder is obtained.
(II) preparing vanadium sodium phosphate electrode plate
20 mg of PVDF is dissolved in 2 mL of NMP, 40 mg conductive carbon black and 140 mg sodium vanadium phosphate are slowly added with stirring, the slurry is coated on aluminum foil by a coating machine according to the thickness of 0.9mm after stirring for 24 hours, and then the aluminum foil is dried for 1 hour under vacuum at 100 ℃ to obtain the sodium vanadium phosphate electrode plate.
(III) preparation of sodium ion Battery
Cutting a sodium vanadium phosphate electrode plate to obtain a wafer with the diameter of 12mm, compacting the wafer by a tablet press under the compaction pressure of 10Mpa, then taking the sodium metal plate with the diameter of 12mm and the thickness of 0.2mm as a cathode by taking the sodium metal plate with the diameter of 12mm as the cathode, taking 0.1mL of 1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution as electrolyte, taking a polypropylene film with the diameter of 19mm as a diaphragm, and assembling the polypropylene film in a glove box filled with high-purity argon to obtain the CR2016 button cell, and charging and discharging the cell on a cell test platform by using the current density of 100 mA/g.
In summary, the invention provides a method for preparing a high-performance vanadium sodium phosphate positive electrode composite material (Na 3V2 (PO 4) 3/C) by combining a ball milling assisted hydrothermal method with an annealing calcination sintering method, and the vanadium sodium phosphate material is applied to the positive electrode of a sodium ion battery, so that the complexity of preparing a novel vanadium sodium phosphate composite material of NASICON by a traditional chemical synthesis method is simplified, the difficulty of low conductivity of the material is overcome, and a sodium ion battery with high specific capacity and excellent cycle stability is obtained by relying on the NASICON type vanadium sodium phosphate. The sodium vanadium phosphate electrode has high capacity, has initial specific capacity of up to 107.4 mA h/g under the current density of 100mA/g, is close to theoretical specific capacity and good in cycling stability, and the capacity is still kept to be equivalent to the initial state after 100 times of cycling charge and discharge.
Claims (4)
1. The preparation method of the vanadium sodium phosphate sodium ion battery anode material is characterized by comprising the following steps:
weighing 2.3396g of ammonium metavanadate, 4.6803g of sodium dihydrogen phosphate dihydrate and 3.9634 g of glucose, adding 30mL ethanol solution, mixing, and drying in a vacuum oven at 80 ℃ for 14 hours at a ball milling speed of 1800rpm for 48 hours to obtain blue/bluish vanadium sodium phosphate precursor slurry, wherein the bluish vanadium sodium phosphate precursor slurry is dried in the oven at 80 ℃ for 2 hours to obtain bluish vanadium sodium phosphate precursor powder;
weighing 5 g of sodium vanadium phosphate precursor powder, placing in a 100 ml beaker, adding 70 ml deionized water, sealing a sealing film, placing on a magnetic stirrer, setting the rotating speed to be 600rpm, setting the temperature to be 75 ℃, fully stirring for 30 min, taking out suspension liquid in a high-pressure hydrothermal reaction kettle, setting the hydrothermal temperature to be 200 ℃, setting the time to be 24 h, setting a vacuum oven to be 120 ℃ after the reaction is finished, and setting the time to be 12 h to obtain a sodium vanadium phosphate precursor;
step three, putting the sodium vanadium phosphate precursor into a tube furnace according to the volume ratio Ar/H 2 And taking the mixed gas with the temperature of 95/5 as a reducing atmosphere, heating to 350 ℃ at a heating rate of 4 ℃/min, sintering for 1 hour, continuously heating to 750 ℃ at the same heating rate, and sintering at constant temperature for 4 hours to obtain black sodium vanadium phosphate powder.
2. The positive electrode material of the sodium vanadium phosphate ion battery is characterized in that: vanadium phosphate nano-powder is obtained by the preparation method of claim 1.
3. The vanadium phosphate nano electrode plate is characterized in that: dissolving 10-50-mg PVDF in 2 mL NMP, adding 10-100 mg conductive carbon black and 10-300-mg sodium vanadium phosphate powder according to claim 2 under magnetic stirring, stirring for 0.5-24 hours uniformly to obtain mixed electrode slurry, coating the slurry on aluminum foil according to the thickness of 0.3-0.9mm by an automatic coating machine, placing the aluminum foil in a vacuum oven, drying for 1-24 hours under 80-120 ℃ under the air pressure of-0.1 Mpa in the oven to obtain the sodium vanadium phosphate electrode plate.
4. A sodium ion battery characterized by: cutting the sodium vanadium phosphate electrode plate according to claim 3 to obtain a wafer with the diameter of 12mm, compacting the wafer by a tablet press, wherein the compaction pressure is 10Mpa, then using the sodium metal plate with the diameter of 12mm and the thickness of 0.2mm as a cathode, using 0.1mL of 1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution as an electrolyte, using a polypropylene film with the diameter of 19mm as a diaphragm, and assembling the wafer in a glove box filled with high-purity argon gas to obtain the button cell.
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| CN105336924A (en) * | 2015-09-25 | 2016-02-17 | 中南大学 | Preparation method of carbon coated vanadium sodium phosphate positive electrode material |
| JP2019220250A (en) * | 2018-06-15 | 2019-12-26 | 一般財団法人電力中央研究所 | Method for manufacturing all-solid battery and all-solid battery |
| CN111293307A (en) * | 2018-12-06 | 2020-06-16 | 中国科学院大连化学物理研究所 | Carbon-supported sodium vanadium fluorophosphate and preparation and application thereof |
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| CN105336924A (en) * | 2015-09-25 | 2016-02-17 | 中南大学 | Preparation method of carbon coated vanadium sodium phosphate positive electrode material |
| JP2019220250A (en) * | 2018-06-15 | 2019-12-26 | 一般財団法人電力中央研究所 | Method for manufacturing all-solid battery and all-solid battery |
| CN111293307A (en) * | 2018-12-06 | 2020-06-16 | 中国科学院大连化学物理研究所 | Carbon-supported sodium vanadium fluorophosphate and preparation and application thereof |
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