CN106920946B - Preparation method of aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material - Google Patents
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Abstract
The invention provides an alumina and carbon composite coated sodium vanadium fluorophosphate cathode material and a preparation method thereof, wherein oxalic acid H is used2C2O4Dissolving sodium fluoride NaF, a vanadium source and a phosphorus source in deionized water, stirring at 60 ℃ to form gel, drying, and presintering the powder in a tube furnace to obtain a precursor; adding a carbon source into the precursor, performing ball milling, drying, calcining in a tubular furnace under the nitrogen atmosphere, and sieving to obtain a carbon-coated sodium vanadium fluorophosphate cathode material; ultrasonically dispersing carbon-coated sodium vanadium fluorophosphate in deionized water uniformly, and adding aluminum nitrate Al (NO) nonahydrate3)3·9H2O ultrasonic treatment for 20 min, stirring for 30 min, and adding ammonia NH3·H2And O, continuously stirring for 1.5 hours at the temperature of 60 ℃, then carrying out suction filtration, washing for multiple times by using deionized water, drying, finally carrying out final firing in a tubular furnace, cooling, and sieving to obtain the aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material.
Description
Technical Field
The invention relates to an aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material and a preparation method thereof, belonging to the field of electrochemical power sources.
Background
In recent years, with the widespread use of lithium ion batteries in the portable electronic market, and particularly the rapid development of the electric automobile market, lithium resources are consumed in large quantities and are about to be depleted. Therefore, sodium ion batteries using abundant, low-cost, and widely distributed sodium as a basic raw material have received much attention. Similar to lithium ion batteries, sodium ion batteries also have a rocking chair type working principle, and sodium ions move back and forth between a positive electrode and a negative electrode in the charging and discharging processes. Sodium ion batteries have many potential advantages over lithium ion batteries, such as: sodium is the sixth most abundant element on earth, and is about 2.74% in the earth's crust and is present in sea water in large quantities; the sodium ion battery can utilize electrolyte solvent and electrolyte salt with lower decomposition potential, and the selection range of the electrolyte is wider; has more stable electrochemical performance and higher safety. Therefore, sodium ion batteries are considered as the next generation secondary batteries most promising as replacements for lithium ion batteries.
Vanadium sodium fluorophosphate (Na) as a positive electrode material for sodium-ion batteries3V2(PO4)2F3) The nano-porous structure has an open three-dimensional NASICON structure, can generate a large gap space suitable for rapid migration of sodium ions, and can improve the dynamic characteristics of the sodium ions with larger radius and weight in the electrochemical migration process; meanwhile, the material has the common characteristics of polyanion type anode materials, and the crystal structure is stable, flexible and controllable in charge and discharge potential. However, in the NASICON structure, VO6Octahedral polyanion group PO4Tetrahedral separation, resulting in a material with less electronic conductivity; further, Na3V2(PO4)2F3Higher voltage is needed in the charge and discharge process, so that some side reactions are easy to occur between the active material and the electrolyte, and the cycle performance of the material is reduced. Therefore, the aluminum oxide and the carbon composite coating layer can reduce Na by introducing the aluminum oxide to modify the sodium vanadium fluorophosphate/carbon cathode material3V2(PO4)2F3The contact with the electrolyte inhibits the occurrence of side reaction between the active substance and the electrolyte, and stabilizes the material structure, thereby improving the cycling stability of the material; the aluminum oxide and carbon composite coating can also effectively reduce the interface resistance of the active substance/electrolyte and improve the de-intercalation speed of sodium ions, thereby reducing the polarization of the active material under high rate and effectively improving Na3V2(PO4)2F3The magnification capacity of (2).
Disclosure of Invention
The invention aims to provide an alumina and carbon composite coated sodium vanadium fluorophosphate cathode material (marked as NVPF/C-Al, N, V, P, F, C, Al respectively represents sodium, vanadium, phosphorus, fluorine, carbon and alumina). The NVPF/C-Al cathode material is prepared from oxalic acid H2C2O4Sodium fluorideNaF, vanadium pentoxide V2O5(or ammonium metavanadate NH)4VO3) Ammonium dihydrogen phosphate NH4H2PO4(or diammonium hydrogen phosphate (NH)4)2HPO4) Glucose C6H12O6(or sucrose C)12H22O11) Aluminum nitrate nonahydrate Al (NO)3)3·9H2O and ammonia NH3·H2O。
The mol ratio of the oxalic acid to the sodium fluoride to the vanadium pentoxide to the ammonium dihydrogen phosphate is 4.5:3:1: 2.
The purity of the oxalic acid, the sodium fluoride, the vanadium pentoxide, the ammonium dihydrogen phosphate and the aluminum nitrate nonahydrate is more than 99 percent.
The preparation method comprises the following steps:
(1) dissolving oxalic acid, sodium fluoride, a vanadium source and a phosphorus source in deionized water, stirring at 60 ℃ to form gel, drying the gel, and pre-burning in a tubular furnace to obtain a precursor;
(2) adding a carbon source into the precursor, ball-milling for 1-3 hours by taking absolute ethyl alcohol as a medium, drying, calcining the obtained powder in a tubular furnace, and sieving to obtain a carbon-coated sodium vanadium fluorophosphate cathode material;
(3) ultrasonically dispersing carbon-coated sodium vanadium fluorophosphate in deionized water uniformly, and adding aluminum nitrate Al (NO) nonahydrate3)3·9H2O, ultrasonic treating for 20 minutes, stirring for 30 minutes, and adding ammonia NH3·H2Continuously stirring for 1.5 hours at the temperature of 60 ℃, then carrying out suction filtration, washing for multiple times by using deionized water, drying, finally burning the obtained powder in a tubular furnace, cooling, and then sieving to obtain the aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material; (4) stirring the aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material with acetylene black and polyvinylidene fluoride (PVDF) to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to prepare an aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material pole piece.
The mol mass ratio of the oxalic acid to the sodium fluoride to the vanadium source to the phosphorus source is 3-5: 1-4: 0.5-2: 1-3, wherein the adding amount of the carbon source is 5-15 wt.% of the mass of the precursor obtained after the first-step sintering, and the adding amount of the aluminum nitrate nonahydrate is 0.5-5 wt.% of the mass of the sample.
More preferably, the molar mass ratio of oxalic acid, sodium fluoride, vanadium source and phosphorus source is 4.5:3:1: and 2, the adding amount of the carbon source is 9 wt% of the mass of the precursor obtained after the first-step sintering, and the adding amount of the aluminum nitrate nonahydrate is 2 wt% of the mass of the sample.
The vanadium source is vanadium pentoxide V2O5Or ammonium metavanadate NH4VO3The phosphorus source is ammonium dihydrogen phosphate NH4H2PO4Or diammonium hydrogen phosphate (NH)4)2HPO4The carbon source is glucose C6H12O6Or sucrose C12H22O11。
Sintering for 4-8 hours at 300-400 ℃ in a nitrogen or argon atmosphere in the step (1); sintering the mixture for 8 to 12 hours at 650 to 750 ℃ in a nitrogen or argon atmosphere; and (3) sintering for 1-3 hours at 550-650 ℃ in a nitrogen or argon atmosphere.
The aluminum oxide and carbon composite coated sodium vanadium fluorophosphate (NVPF/C-Al) anode material has the following remarkable characteristics:
(1) the process is simple (the aluminum oxide and carbon composite coated sodium fluorophosphate NVPF/C-Al cathode material can be obtained only by uniformly mixing carbon coated sodium fluorophosphate NVPF/C with aluminum nitrate nonahydrate and then sintering at a certain temperature for 1-3 hours);
(2) the material has good cycle performance (the aluminum oxide and carbon composite coating layer can effectively reduce the contact between the matrix and the electrolyte, inhibit the occurrence of side reaction between the active substance and the electrolyte and improve the structural stability of the material);
(3) the material has high rate capacity (the interface resistance of the active substance/electrolyte can be effectively reduced by the composite coating of the alumina and the carbon, and the polarization is reduced).
Drawings
FIG. 1 is an X-ray diffraction pattern of the sample NVPF/C of comparative example 1 and the sample NVPF/C-Al of example 2.
FIG. 2 is a charge-discharge curve at 1C for NVPF/C-Al sample of example 2.
The specific implementation mode is as follows:
the essential features and advantages of the present invention are further illustrated by the following description of examples and comparative examples. For convenience of description, the comparative examples will be described first, and then the examples will be described, in comparison with which the effects of the present invention will be shown.
Comparative example 1
Dissolving oxalic acid, sodium fluoride, vanadium pentoxide and ammonium dihydrogen phosphate in deionized water at a molar ratio of 4.5:3:1:2, stirring at 60 ℃ to form gel, drying, and presintering at 350 ℃ for 6 hours in a nitrogen atmosphere to obtain a precursor; adding 9 wt.% of glucose into the precursor, ball-milling for 2 hours, and drying in a 50 ℃ oven; sintering the obtained powder for 10 hours at 700 ℃ in a tubular furnace under the nitrogen atmosphere; after cooling, grinding and sieving are carried out, thus obtaining the NVPF/C positive electrode material. Stirring the obtained NVPF/C, acetylene black and polyvinylidene fluoride (PVDF) into slurry according to the mass ratio of 75:15:10, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain the positive electrode material pole piece of the sodium-ion battery. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and GradeGF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1: 1) is a battery assembled by the electrolyte, and the voltage range is 3.0-4.6V. The first discharge specific capacity of the material 1C was 104.4 mAh g-1The specific discharge capacity is maintained at 98.1 mAh g after 100 cycles-1The capacity retention was only 94.0%.
Example 1
Dissolving oxalic acid (11.3459 g), sodium fluoride (2.5193 g), vanadium pentoxide (4.6010 g) and ammonium dihydrogen phosphate (3.6376 g) in deionized water, stirring at 60 ℃ to form gel, drying, and presintering at 350 ℃ for 6 hours in a nitrogen atmosphere to obtain a precursor; adding 0.45 g of glucose into 5 g of the precursor, ball-milling for 2 hours, and drying in a 50 ℃ oven; sintering the obtained powder for 10 hours at 700 ℃ in a tubular furnace under the nitrogen atmosphere; after cooling, grinding and sieving are carried out, thus obtaining the NVPF/C positive electrode material. Adding 1g NVPF/C into 50 ml deionized water, performing ultrasonic treatment for 40 minutes, stirring to form a black suspended matter, and adding0.01g of aluminum nitrate nonahydrate Al (NO) was added3)3·9H2O, ultrasonic treating for 20 minutes, stirring for 30 minutes, and adding ammonia NH3·H2And O, continuously stirring for 1.5 hours at the temperature of 60 ℃, then carrying out suction filtration, washing for multiple times by using deionized water, then drying, sintering the obtained powder for 2 hours at the temperature of 600 ℃ in a tubular furnace, cooling, and then sieving to obtain the aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material. Stirring the obtained aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 75:15:10 to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to prepare a sodium ion battery cathode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and GradeGF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1: 1) is a battery assembled by the electrolyte, and the voltage range is 3.0-4.6V. The first discharge specific capacity of the material 1C was 111.3 mAh g-1After 100 cycles, the specific discharge capacity is maintained at 104.9 mAh g-1The capacity retention was only 94.2%.
Example 2
Dissolving oxalic acid (11.3459 g), sodium fluoride (2.5193 g), vanadium pentoxide (4.6010 g) and ammonium dihydrogen phosphate (3.6376 g) in deionized water, stirring at 60 ℃ to form gel, drying, and presintering at 350 ℃ for 6 hours in a nitrogen atmosphere to obtain a precursor; adding 0.45 g of glucose into 5 g of the precursor, ball-milling for 2 hours, and drying in a 50 ℃ oven; sintering the obtained powder for 10 hours at 700 ℃ in a tubular furnace under the nitrogen atmosphere; after cooling, grinding and sieving are carried out, thus obtaining the NVPF/C positive electrode material. Adding 1g NVPF/C into 50 ml deionized water, performing ultrasonic treatment for 40 minutes, stirring to form a black suspension, and adding 0.02g aluminum nitrate Al (NO) nonahydrate3)3·9H2O, ultrasonic treating for 20 minutes, stirring for 30 minutes, and adding ammonia NH3·H2And O, continuously stirring for 1.5 hours at the temperature of 60 ℃, then carrying out suction filtration, washing for multiple times by using deionized water, then drying, sintering the obtained powder for 2 hours at the temperature of 600 ℃ in a tubular furnace, cooling, and then sieving to obtain the aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material. Coating the obtained alumina and carbon with vanadium fluorophosphate in a composite wayStirring the sodium anode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 75:15:10 to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to prepare the anode material pole piece of the sodium-ion battery. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and GradeGF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1: 1) is a battery assembled by the electrolyte, and the voltage range is 3.0-4.6V. The first discharge specific capacity of the material 1C was 124.4 mAh g-1After 100 cycles, the discharge specific capacity is maintained at 114.0 mAh g-1The capacity retention was only 91.6%.
Example 3
Dissolving oxalic acid (11.3459 g), sodium fluoride (2.5193 g), vanadium pentoxide (4.6010 g) and ammonium dihydrogen phosphate (3.6376 g) in deionized water, stirring at 60 ℃ to form gel, drying, and presintering at 350 ℃ for 6 hours in a nitrogen atmosphere to obtain a precursor; adding 0.45 g of glucose into 5 g of the precursor, ball-milling for 2 hours, and drying in a 50 ℃ oven; sintering the obtained powder for 10 hours at 700 ℃ in a tubular furnace under the nitrogen atmosphere; after cooling, grinding and sieving are carried out, thus obtaining the NVPF/C positive electrode material. Adding 1g NVPF/C into 50 ml deionized water, performing ultrasonic treatment for 40 minutes, stirring to form a black suspension, and adding 0.03g aluminum nitrate Al (NO) nonahydrate3)3·9H2O, ultrasonic treating for 20 minutes, stirring for 30 minutes, and adding ammonia NH3·H2And O, continuously stirring for 1.5 hours at the temperature of 60 ℃, then carrying out suction filtration, washing for multiple times by using deionized water, then drying, sintering the obtained powder for 2 hours at the temperature of 600 ℃ in a tubular furnace, cooling, and then sieving to obtain the aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material. Stirring the obtained aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 75:15:10 to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to prepare a sodium ion battery cathode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and GradeGF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1: 1) is a battery assembled by the electrolyte, and the voltage range is 3.0-4.6V. The specific capacity of initial discharge of the material 1C was 107.9 mAh g-1After 100 times of circulation, the specific discharge capacity is maintained at 92.1 mAh g-1The capacity retention was only 85.4%.
Claims (1)
1. A preparation method of an aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material is characterized by comprising the following specific steps:
11.3459 g of oxalic acid, 2.5193 g of sodium fluoride, 4.6010 g of vanadium pentoxide and 3.6376 g of ammonium dihydrogen phosphate are dissolved in deionized water, stirred at 60 ℃ to form gel, dried and presintered at 350 ℃ for 6 hours in a nitrogen atmosphere to obtain a precursor; adding 0.45 g of glucose into 5 g of the precursor, ball-milling for 2 hours, and drying in a 50 ℃ oven; sintering the obtained powder for 10 hours at 700 ℃ in a tubular furnace under the nitrogen atmosphere; after cooling, grinding and sieving to obtain a carbon-coated sodium vanadium fluorophosphate cathode material; adding 1g of carbon-coated sodium vanadium fluorophosphate cathode material into 50 ml of deionized water, performing ultrasonic treatment for 40 minutes, stirring to form a black suspended substance, and adding 0.02g of aluminum nitrate Al (NO) nonahydrate3)3·9H2O, ultrasonic treating for 20 minutes, stirring for 30 minutes, and adding ammonia NH3·H2And O, continuously stirring for 1.5 hours at the temperature of 60 ℃, then carrying out suction filtration, washing for multiple times by using deionized water, then drying, sintering the obtained powder for 2 hours at the temperature of 600 ℃ in a tubular furnace, cooling, and then sieving to obtain the aluminum oxide and carbon composite coated sodium vanadium fluorophosphate cathode material.
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| CN109755489B (en) * | 2017-11-08 | 2022-07-05 | 中国科学院大连化学物理研究所 | Preparation of sodium vanadium fluorophosphate/carbon compound and application of compound |
| CN109841802A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of carbon coating Na3V2(PO4)2F3Compound and its preparation and application |
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| CN111525130A (en) * | 2020-05-11 | 2020-08-11 | 金国辉 | Modified Na3V2(PO4)2F3The positive electrode material of sodium ion battery and the preparation method |
| CN113130903B (en) * | 2021-04-14 | 2022-11-29 | 陕西科技大学 | Aluminum oxide coated iron cyanamide material prepared by sol-gel method and preparation method and application thereof |
| CN114094066A (en) * | 2021-10-29 | 2022-02-25 | 江苏大学 | Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery |
| CN114335444A (en) * | 2021-12-16 | 2022-04-12 | 江苏海基新能源股份有限公司 | Sodium-ion battery positive electrode material Na3V2(PO4)2F3Preparation method of/C |
| CN114824250B (en) * | 2022-01-17 | 2024-05-03 | 常州大学 | Multifunctional additive synchronous modified carbon-coated vanadium sodium fluorophosphate composite material, preparation method and application thereof |
| CN115050931A (en) * | 2022-05-24 | 2022-09-13 | 新疆师范大学 | Preparation method of nitrogen and sulfur co-doped carbon layer for coating positive electrode of sodium ion battery |
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