CN109950536B - Method for preparing sodium vanadium phosphate nanofiber anode material - Google Patents
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Abstract
The invention discloses a method for preparing a sodium vanadium phosphate nanofiber anode material, which comprises the steps of weighing a sodium source, a vanadium source, a phosphorus source and a high-molecular weight according to stoichiometric ratioMixing and stirring the sub-polymer, the reducing agent and the solvent uniformly to obtain electrostatic spinning solution, carrying out electrostatic spinning to obtain nanofiber precursor, carrying out heat treatment under non-oxidizing atmosphere, and cooling to obtain Na 3 V 2 (PO 4 ) 3 and/C positive electrode material. The preparation method provided by the invention reduces the cost of raw materials, and the prepared one-dimensional nano wire is uniform and continuous, has smooth surface and non-spindle-shaped protrusions, improves the structural stability of the positive electrode material in the charge and discharge process, and is beneficial to improving the cycle performance of the positive electrode material.
Description
Technical Field
The invention belongs to the field of electrode materials and the field of electrochemical energy storage, and relates to a sodium ion battery anode material sodium vanadium phosphate (Na) 3 V 2 (PO 4 ) 3 ) In particular to a method for preparing a sodium vanadium phosphate nanofiber anode material.
Background
The development of high-performance energy storage devices is an indispensable part of renewable energy utilization, and lithium ion batteries have been widely used in various energy storage devices due to their excellent energy storage performance. With the increasing demand for energy storage, the problem of lithium resource shortage is increasingly prominent, and sodium ion batteries are expected to become substitutes for the lithium ion batteries. The sodium ion battery has the advantages of low cost of electrode materials, wide sources of raw materials, low price, easy obtainment and the like. However, due to sodium ion radius
Greater than lithium ion radius->
Their ionic conductivity is relatively low, resulting in their electrochemical performance being less than ideal.
NASICON type Na 3 V 2 (PO 4 ) 3 Is composed of [ VO 6 ]Octahedron and [ PO 4 ]The three-dimensional structure skeleton formed by tetrahedra is formed, so that the structure skeleton has a rapid channel for Na ion deintercalation, and Na with higher ion conductivity and good structural stability 3 V 2 (PO 4 ) 3 Is a sodium ion battery anode material with development prospect. Despite the above advantages, na 3 V 2 (PO 4 ) 3 The lower electron conductivity limits the exertion of its electrochemical properties. In general, the electrochemical performance of the electrode material can be further improved by coating the conductive material. In addition, reducing the particle size of the material can effectively shorten the sodium ion migration path. Therefore, particle nanocrystallization is also an important approach to improving rate performance for the material itself. At present, electrostatic spinning is widely accepted as an effective way for obtaining nano materials, and the method is simple, convenient and environment-friendly and has been successfully applied to preparing LiFePO 4 、Li 4 Ti 5 O 12 And LiNi 0.5 Mn 1.5 O 4 A material for a plasma lithium ion battery. The conductive material is added into the nanofiber, so that the conductivity is increased, and meanwhile, the structural damage caused by the charge and discharge process can be reduced. And the conductive network structure constructed by the one-dimensional nano fiber also provides a rapid channel for sodium ion transmission of the electrode material. It has been reported in the literature that this approach is effective in improving phosphate materials (e.g., li) 3 V 2 (PO 4 ) 3 ) Is used for the electrochemical performance of the battery.
The electrochemical performance of the sodium vanadium phosphate nanofiber prepared by electrostatic spinning is greatly affected by the factors of the structure, the size and the surface morphology, and spindle-shaped particles are easy to appear, so that the sodium vanadium phosphate nanofiber is unstable in structure in the charge and discharge process.
Disclosure of Invention
In view of the above, the invention aims to provide a method for preparing a sodium vanadium phosphate nanofiber anode material, which aims to solve the problem of unstable structure in the charging and discharging process of the sodium vanadium phosphate nanofiber prepared by the conventional electrostatic spinning.
According to the method, when the vanadium sodium phosphate nanofiber anode material is prepared by electrostatic spinning, a reducing agent is added in the preparation process of the spinning solution, and the viscosity and the conductivity of the spinning solution are adjusted by pre-reduction, so that the components of a spinning precursor and a final product are uniform, and the surface is smooth.
Specifically, the method for preparing the vanadium sodium phosphate nanofiber anode material comprises the following steps of:
s1, weighing a sodium source, a vanadium source and a phosphorus source according to a molar ratio Na:V:P=3:2:3, and uniformly mixing and stirring the sodium source, the vanadium source and the phosphorus source with a high polymer, a reducing agent and a solvent to obtain an electrostatic spinning solution for later use;
wherein, the mol ratio of the reducer to the sodium vanadium phosphate is = (0.8-2) to 1; the mass ratio of the high molecular polymer to the sodium vanadium phosphate is = (2.5-4) to 1;
the sodium source is one or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium dihydrogen citrate, sodium oxalate, sodium carbonate, sodium hydroxide and sodium acetate.
The vanadium source is one or more of vanadium dioxide, vanadium pentoxide, ammonium vanadate, ammonium metavanadate, sodium metavanadate and sodium vanadate.
The phosphorus source is one or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, diammonium phosphate, monoammonium phosphate, triammonium phosphate and phosphoric acid.
The reducing agent is one or more of citric acid, oxalic acid, tartaric acid, oxalic acid, adipic acid, malonic acid, ascorbic acid, sucrose, mandelic acid, malic acid, formaldehyde, acetaldehyde, n-butyraldehyde, isobutyraldehyde, tetraethyl glycol, isopropanol, hydrazine hydrate and urea.
The reducing agent can reduce pentavalent vanadium, and adjust the viscosity and the conductivity of the spinning solution, thereby influencing the components and the morphology of the precursor and the product.
The solvent is one or more of water, absolute ethyl alcohol, acetic acid, hexafluoroisopropanol, dimethylformamide, triethanolamine, hexafluoroacetone, chloroform and tetrahydrofuran.
S2, carrying out electrostatic spinning on the electrostatic spinning solution obtained in the step S1 to obtain a nanofiber precursor for later use;
the electrostatic spinning voltage is 8-25 kV, the distance between a filament outlet and a receiver is 10-35 cm, the spinning speed is 0.01-3 mm/min, and the rotating speed of the receiver is 1-10 m/h.
Preferably, the voltage of the electrostatic spinning is 10-15 kV, the distance between a filament outlet and a receiver is 12-20 cm, the spinning speed is 0.05-0.5 mm/min, and the rotating speed of the receiver is 4-7 m/h.
S3, carrying out heat treatment on the nanofiber precursor obtained in the S2 in a non-oxidizing atmosphere, and cooling to obtain Na 3 V 2 (PO 4 ) 3 and/C positive electrode material.
The non-oxidizing atmosphere is one or more of argon, helium, neon, nitrogen and hydrogen.
The heat treatment temperature is 500-850 ℃, and the calcination time is 1-24 h.
Compared with the prior art, the technical scheme provided by the invention has the beneficial effects that:
1. after the reducing agent is added into the spinning solution, the viscosity and the conductivity of the spinning solution can be adjusted to achieve proper balance. The balance of viscosity and conductivity is an important factor for determining the shape of the precursor, and the addition of the reducing agent can ensure that the prepared one-dimensional nano wire is uniform and continuous, has smooth surface and is non-spindle-shaped, so that the structural stability of the material in the charge and discharge processes is improved.
2. The reducing agent is used as a carbon source to realize in-situ carbon coating, so that the electron conductivity of the sodium vanadium phosphate is enhanced; the growth of the crystal grains of the active material can be inhibited, the agglomeration of the crystal grains can be prevented, and the rate capability of the battery is improved; in addition, the active substance can be prevented from separating from the current collector due to repeated volume expansion/contraction in the charge and discharge process, and the cycle performance of the active substance can be improved.
3. The reducing agent is added in the preparation process of the spinning solution, so that the pentavalent vanadium ions in the raw materials can be reduced to trivalent in advance under the conditions of normal temperature and normal pressure. The use of expensive trivalent vanadium sources as raw materials is avoided, and the cost of raw materials is reduced. Since vanadium has been reduced at normal temperature, the temperature required for the subsequent heat treatment of the precursor is significantly reduced and the time is also significantly shortened.
Drawings
FIG. 1 is Na obtained by the preparation of example 1 3 V 2 (PO 4 ) 3 X-ray diffraction (XRD) pattern of/C;
FIG. 2 is Na obtained by the preparation of example 1 3 V 2 (PO 4 ) 3 Scanning electron microscope image of/C;
FIG. 3 is Na obtained by comparative example 2 3 V 2 (PO 4 ) 3 Scanning electron microscope image of/C;
FIG. 4 is a Na obtained by the preparation of example 1 3 V 2 (PO 4 ) 3 A first charge-discharge curve graph of the battery under different multiplying powers;
FIG. 5 is Na obtained by comparative example 2 3 V 2 (PO 4 ) 3 A first charge-discharge curve graph of the battery under different multiplying powers;
FIG. 6 is a graph showing the variation of the conductivity and viscosity of the spinning solution prepared in example 6 with the amount of oxalic acid added.
Detailed Description
The following describes the technical solution in the embodiment of the present invention in detail with reference to the drawings in the embodiment of the present invention.
Example 1
a. Weighing sodium dihydrogen phosphate and ammonium metavanadate according to the molar ratio of Na to V to P=3 to 2 to 3, weighing oxalic acid according to the molar ratio of oxalic acid to sodium vanadium phosphate=1 to 1, stirring the solution at room temperature by taking deionized water as a solvent until the solution is completely dissolved, adding polyvinylpyrrolidone with the mass ratio of 3 to 1 (high polymer to sodium vanadium phosphate) and the average molecular weight of 1300000, and continuously stirring the mixture until uniform spinning solution is formed.
b. Extracting the spinning solution into a 5mL syringe, and installing a spinning needle, wherein the distance between the needle and the aluminum foil is 15cm, and the voltage is 12kV; spinning speed is 0.1mm/min; the rotating speed of the receiver is 5m/h, and the one-dimensional nanofiber precursor is prepared.
c. Placing the collected nanofiber precursor into a tube furnace, heating to 650 ℃ at a speed of 5 ℃/min under the argon atmosphere, keeping the temperature for 10 hours, and cooling to the temperature after heat treatmentAt room temperature, na is obtained 3 V 2 (PO 4 ) 3 and/C nanofiber positive electrode material.
Example 2
a. Weighing sodium dihydrogen phosphate and ammonium metavanadate according to the molar ratio of Na to V to P=3 to 2 to 3, weighing oxalic acid according to the molar ratio of oxalic acid to sodium vanadium phosphate=1 to 1, stirring the solution at room temperature by taking deionized water as a solvent until the solution is completely dissolved, adding polyvinylpyrrolidone with the mass ratio of 3 to 1 (high polymer to sodium vanadium phosphate) and the average molecular weight of 1300000, and continuously stirring the mixture until uniform spinning solution is formed.
b. Extracting the spinning solution into a 5mL syringe, and installing a spinning needle, wherein the distance between the needle and the aluminum foil is 15cm, and the voltage is 12kV; spinning speed is 0.1mm/min; the rotating speed of the receiver is 5m/h, and the one-dimensional nanofiber precursor is prepared.
c. Placing the collected nanofiber precursor into a tube furnace, heating to 650 ℃ at a speed of 5 ℃/min under the argon atmosphere, keeping the temperature for 10 hours, cooling to room temperature after heat treatment, and obtaining Na 3 V 2 (PO 4 ) 3 and/C nanofiber positive electrode material.
d. Dissolving 0.2mL of aniline monomer in 0.1M 100mL of hydrochloric acid solution, adding the product prepared in the step c while stirring, uniformly dispersing by ultrasonic, weighing ammonium persulfate with the molar ratio of 1.2:1 to aniline, dissolving in 0.1M 50mL of hydrochloric acid solution, dropwise adding the ammonium persulfate solution into aniline-hydrochloric acid-sodium vanadium phosphate nanofiber under the condition of ice-water bath, and stirring for reacting for 5 hours to obtain suspension.
e. Transferring the suspension prepared in the step d to a vacuum drying oven at 60 ℃ for drying for 24 hours to finally obtain the composite anode material Na 3 V 2 (PO 4 ) 3 C/PANI (PANI in Na 3 V 2 (PO 4 ) 3 The mass percentage of the composite nano-fiber of/C/PANI is 10 percent).
Example 3
a. Weighing sodium carbonate, vanadium pentoxide and phosphoric acid according to the molar ratio of Na to V to P=3 to 2 to 3, weighing citric acid according to the molar ratio of citric acid to sodium vanadium phosphate=2 to 1, stirring to be completely dissolved at room temperature by taking dimethylformamide as a solvent, adding polyvinyl alcohol with the mass ratio of 2.5 to 1 (high polymer to sodium vanadium phosphate) and the average molecular weight of 6000, and continuously stirring to form uniform spinning solution.
b. Extracting the spinning solution into a 5mL syringe, and installing a spinning needle, wherein the distance between the needle and the aluminum foil is 10cm, and the voltage is 8kV; spinning speed is 3mm/min; the rotating speed of the receiver is 3m/h, and the one-dimensional nanofiber precursor is prepared.
c. Placing the collected nanofiber precursor into a tube furnace, heating to 750 ℃ at 5 ℃/min under the argon atmosphere, keeping the temperature for 1h, cooling to room temperature after heat treatment, and obtaining Na 3 V 2 (PO 4 ) 3 and/C nanofiber positive electrode material.
Example 4
a. Sodium oxalate and metavanadate are weighed according to the molar ratio of Na to V to P=3 to 2 to 3, diammonium hydrogen phosphate and ascorbic acid are weighed according to the molar ratio of ascorbic acid to sodium vanadium phosphate=0.8 to 1, water is taken as a solvent, stirring is carried out at the temperature of 30 ℃ until the ascorbic acid is completely dissolved, then polyethylene oxide with the mass ratio of 4 to 1 (high polymer to sodium vanadium phosphate) and the average molecular weight of 600000 is added, and stirring is continued until uniform spinning solution is formed.
b. Extracting the spinning solution into a 5mL syringe, and installing a spinning needle, wherein the distance between the needle and the aluminum foil is 35cm, and the voltage is 20kV; spinning speed is 0.01mm/min; the rotating speed of the receiver is 10m/h, and the one-dimensional nanofiber precursor is prepared.
c. Placing the collected nanofiber precursor into a tube furnace, heating to 500 ℃ at a speed of 5 ℃/min under the argon atmosphere, keeping the temperature for 24 hours, cooling to room temperature after heat treatment, and obtaining Na 3 V 2 (PO 4 ) 3 and/C nanofiber positive electrode material.
Example 5
a. Sodium hydroxide, sodium metavanadate and triammonium phosphate are weighed according to the molar ratio Na:V:P=3:2:3, tartaric acid is weighed according to the molar ratio tartaric acid and sodium vanadium phosphate=1.3:1, acetic acid is taken as a solvent, stirring is carried out at the temperature of 30 ℃ until the tartaric acid is completely dissolved, polyvinylpyrrolidone with the mass ratio of 3.3:1 (high polymer: sodium vanadium phosphate) and the average molecular weight of 40000 is added, and stirring is continued until uniform spinning solution is formed.
b. Extracting the spinning solution into a 5mL syringe, and installing a spinning needle, wherein the distance between the needle and the aluminum foil is 25cm, and the voltage is 25kV; spinning speed is 1mm/min; the rotating speed of the receiver is 1m/h, and the one-dimensional nanofiber precursor is prepared.
d. Placing the collected nanofiber precursor into a tube furnace, heating to 850 ℃ at a speed of 5 ℃/min under the argon atmosphere, keeping the temperature for 15 hours, cooling to room temperature after heat treatment, and obtaining Na 3 V 2 (PO 4 ) 3 and/C nanofiber positive electrode material.
Example 6
Weighing sodium dihydrogen phosphate and ammonium metavanadate according to the molar ratio of Na to V to P=3 to 2 to 3, respectively weighing oxalic acid to sodium vanadium phosphate=0 to 1, 0.5 to 1, 1 to 1, 1.2 to 1, 1.5 to 1, 2 to 1 and 2.5 to 1, taking deionized water as a solvent, stirring at room temperature until the oxalic acid and the deionized water are completely dissolved, adding polyvinylpyrrolidone with the mass ratio of 3 to 1 (high molecular polymer to sodium vanadium phosphate) and the average molecular weight of 1300000, and continuously stirring until uniform spinning solution is formed.
Comparative example 1
Solid phase method for preparing Na 3 V 2 (PO 4 ) 3 /C：
The stoichiometric ratio of sodium dihydrogen phosphate and ammonium metavanadate were weighed respectively in the same manner as in example 1, polyvinylpyrrolidone having an average molecular weight of 1300000 was mixed in a mortar, and the mixture was put in a ball mill to be subjected to mechanical ball milling at 400rpm for 8 hours to obtain a precursor. The subsequent heat treatment of the precursor was the same as in example 1 (placing the precursor in a tube furnace, heating to 650 ℃ at 5 ℃ C./min under argon atmosphere, keeping the temperature for 10 hours, cooling to room temperature after the heat treatment, and obtaining Na 3 V 2 (PO 4 ) 3 and/C positive electrode material, wherein the carbon content is 8.2%).
Comparative example 2
Preparation of Na without addition of reducing agent by electrostatic spinning method 3 V 2 (PO 4 ) 3 /C：
The preparation method was similar to example 1, except that the addition of a reducing agent (oxalic acid) was not required in the preparation of the dope, and the electrospinning was performed using the obtained dope, and the rest of the steps were the same as in example 1 (carbon content 8.7%).
Weighing sodium dihydrogen phosphate and ammonium metavanadate according to a molar ratio of Na to V to P=3 to 2 to 3, stirring at room temperature with deionized water as a solvent until the sodium dihydrogen phosphate and the ammonium metavanadate are completely dissolved, adding polyvinylpyrrolidone with a mass ratio of 3 to 1 (high polymer to sodium vanadium phosphate) and an average molecular weight of 1300000, and continuously stirring until a uniform spinning solution is formed.
b. Extracting the spinning solution into a 5mL syringe, and installing a spinning needle, wherein the distance between the needle and the aluminum foil is 15cm, and the voltage is 12kV; spinning speed is 0.1mm/min; the rotating speed of the receiver is 5m/h, and the one-dimensional nanofiber precursor is prepared.
c. Placing the collected nanofiber precursor into a tube furnace, heating to 650 ℃ at a speed of 5 ℃/min under the argon atmosphere, keeping the temperature for 10 hours, cooling to room temperature after heat treatment, and obtaining Na 3 V 2 (PO 4 ) 3 and/C nanofiber positive electrode material. )
Preparation of a Battery
The composite materials prepared in examples 1, 2, 3, 4 and 5 and comparative examples 1 and 2 are taken as positive electrode active materials, and are weighed with acetylene black (conductive agent) and PVDF (polyvinylidene fluoride, adhesive) according to the mass ratio of 80:10:10, and then are ground for a period of time in a mortar, uniformly mixed, added with N-methylpyrrolidone (NMP) and continuously ground for a period of time, and finally a uniform black viscous slurry substance is obtained. The uniform slurry obtained after grinding is placed on an aluminum foil, and is uniformly coated into a film with uniform thickness by a scraper. Sodium metal sheet is used as a counter electrode, glass fiber membrane is used as a diaphragm, and 1mol/L NaClO is used as a diaphragm 4 And (3) using PC (propylene carbonate) as electrolyte, and assembling the CR2032 button cell in an anhydrous and anaerobic argon atmosphere glove box. The rate performance and the cycle performance are shown in the following table:
TABLE 1 comparison of rate performance and cycle performance for different samples
Claims (1)
1. The method for preparing the vanadium sodium phosphate nanofiber anode material is characterized by comprising the following steps of:
s1, according to a mole ratio of Na: v: p=3: 2:3, weighing sodium carbonate, vanadium pentoxide and phosphoric acid, and citric acid according to the molar ratio: weighing citric acid by taking sodium vanadium phosphate=2:1, stirring at room temperature by taking dimethylformamide as a solvent until the citric acid is completely dissolved, adding polyvinyl alcohol with the average molecular weight of 6000, wherein the mass ratio of the polyvinyl alcohol to the sodium vanadium phosphate is 2.5:1, and continuously stirring until a uniform spinning solution is formed;
s2, extracting the spinning solution into a 5mL syringe, and installing a spinning needle, wherein the distance between the needle and the aluminum foil is 10cm, and the voltage is 8kV; spinning speed is 3mm/min; the rotating speed of the receiver is 3m/h, and a one-dimensional nanofiber precursor is prepared;
s3, placing the collected nanofiber precursor in a tube furnace, heating to 750 ℃ at 5 ℃/min under the argon atmosphere, keeping the temperature for 1h, and cooling to room temperature after heat treatment to obtain Na 3 V 2 (PO 4 ) 3 and/C nanofiber positive electrode material.
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| CN115818611A (en) * | 2022-12-13 | 2023-03-21 | 大连融科储能集团股份有限公司 | Mg-doped sodium vanadium phosphate, mg-doped sodium vanadium fluorophosphate, and preparation methods and applications thereof |
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