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CN-122025743-A - Low-temperature-resistant high-rate charge-discharge sodium ion startup and shutdown battery and preparation method thereof

CN122025743ACN 122025743 ACN122025743 ACN 122025743ACN-122025743-A

Abstract

The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion startup and shutdown battery resistant to low-temperature high-rate charge and discharge and a preparation method thereof; the method is used for solving the problems that the performance of the existing sodium ion start-stop battery is reduced and the multiplying power performance is poor in a low-temperature environment, and the tantalum doped sodium vanadium oxyfluoride phosphate and the di-terpyridyl polyurethane composite graphene are added into the positive electrode of the sodium ion start-stop battery, and an intermediate product 4 containing the di-terpyridyl and amino is obtained through a series of reactions of 2-bromo-5-nitropyridine and 1-ethoxyvinyl-tributylstannane, and then the intermediate product 4 is reacted with polytetrahydrofuran and dicyclohexylmethane diisocyanate to obtain the di-terpyridyl polyurethane composite graphene, so that the low-temperature resistance of the battery is improved, tantalum ions are doped in sodium vanadium oxyfluoride phosphate, the lattice constant is increased, and the multiplying power performance of the battery is improved, and the sodium ion start-stop battery can still maintain high-efficiency performance output and good stability in a frequent start-stop working mode.

Inventors

  • ZOU WEIMIN
  • ZOU JIAYI
  • CAI HONGFU
  • ZOU WU
  • ZHANG ANNING

Assignees

  • 江苏传艺科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260206

Claims (9)

  1. 1. A low-temperature-resistant high-rate charge-discharge sodium ion start-stop battery is characterized by comprising a positive electrode material and a negative electrode material; The positive electrode material comprises, by weight, 46-92 parts of tantalum doped sodium vanadium oxyfluoride phosphate, 1.5-3 parts of double terpyridyl polyurethane composite graphene and 1.5-3 parts of polyvinylidene fluoride; The negative electrode material comprises, by weight, 47-94 parts of hard carbon, 2.25-4.5 parts of polyacrylic acid and 0.75-1.5 parts of sodium carboxymethylcellulose; The ditylpyridyl polyurethane composite graphene is prepared by the following steps: Step A1, introducing argon into acetonitrile and 2-bromo-5-nitropyridine, and adding 1-ethoxyvinyl-tributylstannane and bis (triphenylphosphine) palladium dichloride to stir to obtain an intermediate product 1; Step A2, reacting the intermediate product 1, tetrahydrofuran, hydrochloric acid and 4-tertiary butyl catechol to obtain an intermediate product 2; step A3, stirring sodium hydroxide, absolute ethyl alcohol, an intermediate product 2 and terephthalaldehyde, dropwise adding ammonia water in an ice bath for reaction to obtain an intermediate product 3; step A4, reacting sodium sulfide, the intermediate product 3 with deionized water, and drying to obtain an intermediate product 4; step A5, dehydrating polytetrahydrofuran, introducing argon, cooling, adding tetrahydrofuran, dibutyltin dilaurate and dicyclohexylmethane diisocyanate for reaction, and adding an intermediate product 4 for reaction to obtain the ditylpyridinium polyurethane; And A6, carrying out ultrasonic treatment on graphene oxide powder and deionized water, dispersing the ditylpyridinium polyurethane in distilled water, adding the distilled water into a flask, carrying out ultrasonic treatment, adding ascorbic acid, stirring, and carrying out sealing reaction to obtain the ditylpyridinium polyurethane composite graphene.
  2. 2. The low temperature and high rate charge and discharge resistant sodium ion start-stop battery according to claim 1, wherein the dosage ratio of acetonitrile, 2-bromo-5-nitropyridine, 1-ethoxyvinyl-tributylstannane and bis (triphenylphosphine) palladium dichloride in step A1 is 250-500ml:43.7-87.4mmol:55.2-110.4mmol:1.7-3.4mmol.
  3. 3. The low-temperature and high-rate charge-discharge resistant sodium ion start-stop battery according to claim 1, wherein the dosage ratio of the intermediate product 1, tetrahydrofuran, hydrochloric acid and 4-tert-butyl catechol in the step A2 is 41.6-83.2 mmol/120-240 mL/40-80 mL/0.1-0.2 g, and the molar concentration of the hydrochloric acid is 2.5mol/L.
  4. 4. The low-temperature and high-rate charge-discharge resistant sodium ion start-stop battery according to claim 1, wherein the dosage ratio of sodium hydroxide, absolute ethyl alcohol, an intermediate product 2, terephthalaldehyde and ammonia water in the step A3 is 1.5-3g:100-200mL:23.4-46.8mmol:6.63-13.26mmol:100-200mL, and the mass fraction of the ammonia water is 25%.
  5. 5. The low temperature and high rate charge and discharge resistant sodium ion start-stop battery according to claim 1, wherein the dosage ratio of sodium sulfide, intermediate product 3 and deionized water in step A4 is 5-10g:5-10g:50-100mL.
  6. 6. The sodium ion start-stop battery with low temperature and high rate charge and discharge resistance according to claim 1, wherein the dosage ratio of polytetrahydrofuran, tetrahydrofuran, dibutyltin dilaurate, dicyclohexylmethane diisocyanate and intermediate 4 in the step A5 is 24-48g:125-250mL:0.09-0.18g:0.0252-0.0504mol:0.0126-0.0252mol, and the model of polytetrahydrofuran is PTMEG-2000.
  7. 7. The sodium ion start-stop battery resistant to low-temperature and high-rate charge and discharge according to claim 1, wherein the dosage ratio of graphene oxide powder, deionized water, di-terpyridyl polyurethane, distilled water and ascorbic acid in the step A6 is 90-180mg:9-18mL:90-180mg:15-30mL:50-100mg.
  8. 8. The low-temperature and high-rate charge-discharge resistant sodium ion start-stop battery according to claim 1, wherein the tantalum doped sodium vanadium fluorophosphate is prepared by the following steps: Stirring sodium metabisulfite and deionized water, dissolving sodium metavanadate in distilled water, adding into a flask, stirring, adding tantalum pentachloride, dissolving ammonium dihydrogen phosphate and sodium fluoride in water, dripping into the flask, stirring, standing, filtering, washing filter residues, centrifuging, and drying to obtain tantalum doped sodium vanadium fluorophosphate; The dosage ratio of sodium metabisulfite, deionized water, sodium metavanadate, distilled water, tantalum pentachloride, ammonium dihydrogen phosphate, sodium fluoride and water is 40-80mmol:40-80mL:20-40mmol:40-80mL:0.00244-0.00488g:60-120mmol:34-68mmol:40-80mL.
  9. 9. A method for preparing a low-temperature and high-rate charge-discharge resistant sodium ion start-stop battery, which is characterized by comprising the following steps of: Firstly, weighing 46-92 parts of tantalum doped fluoroxyvanadium sodium phosphate, 1.5-3 parts of di-terpyridyl polyurethane composite graphene and 1.5-3 parts of polyvinylidene fluoride for standby according to parts by weight, wherein the model of polyvinylidene fluoride is PVDF5130; mixing tantalum doped sodium vanadium fluorophosphate, double terpyridyl polyurethane composite graphene and polyvinylidene fluoride, adding N-methyl pyrrolidone, stirring, coating on a positive electrode current collector, rolling, slitting and die-cutting to obtain a positive electrode plate; weighing 47-94 parts of hard carbon, 2.25-4.5 parts of polyacrylic acid and 0.75-1.5 parts of sodium carboxymethylcellulose for standby according to parts by weight, wherein the type of the polyacrylic acid is PAA1720; Step four, mixing hard carbon, polyacrylic acid and sodium carboxymethyl cellulose, coating on a negative electrode current collector, rolling, slitting and die cutting to obtain a negative electrode plate; And fifthly, winding the positive plate, the negative plate and the polypropylene diaphragm, then filling the wound positive plate, the wound negative plate and the polypropylene diaphragm into a shell, and injecting electrolyte 1M NaPF 6 /EC+DEC+EMC (1:1:1, v/v/v) to obtain the low-temperature and high-rate charge-discharge resistant sodium ion start-stop battery.

Description

Low-temperature-resistant high-rate charge-discharge sodium ion startup and shutdown battery and preparation method thereof Technical Field The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion startup and shutdown battery resistant to low-temperature high-rate charge and discharge and a preparation method thereof. Background Current battery starting and stopping techniques are mainly based on lead-acid batteries, but in cold weather, the performance of lead-acid batteries can be significantly reduced, affecting their role in starting and assisting other electrical appliances of the vehicle. Compared with the traditional lithium ion battery, the electrode materials of the sodium ion battery are different, particularly the ionic radius of sodium ions is larger, so that the diffusion speed and the activity of the sodium ions in the battery are different, and the overall performance is affected. The existing sodium ion startup and shutdown battery has the problems of lower migration rate in the battery and poor performance under low-temperature conditions due to larger radius of sodium ions despite a certain maturity. Therefore, the invention provides the sodium ion start-stop battery resistant to low-temperature high-rate charge and discharge and the preparation method thereof, which improve the performance of the sodium ion battery in a low-temperature environment, simultaneously maintain the high-rate charge and discharge capability and meet the requirements of the automobile start-stop battery. Disclosure of Invention In order to overcome the technical problems, the invention aims to provide a sodium ion start-stop battery resistant to low-temperature high-rate charge and discharge and a preparation method thereof, and solves the problems that the existing sodium ion start-stop battery is poor in rate performance and performance in a low-temperature environment. The aim of the invention can be achieved by the following technical scheme: in a first aspect, the application provides a sodium ion start-stop battery resistant to low-temperature high-rate charge and discharge, which comprises a positive electrode material and a negative electrode material; The positive electrode material comprises, by weight, 46-92 parts of tantalum doped sodium vanadium oxyfluoride phosphate, 1.5-3 parts of double terpyridyl polyurethane composite graphene, 1.5-3 parts of polyvinylidene fluoride and 1-2 parts of graphene; Wherein the negative electrode material comprises the following components, by weight, 47-94 parts of hard carbon, 2.25-4.5 parts of polyacrylic acid and 0.75-1.5 parts of sodium carboxymethyl cellulose; the dual terpyridyl polyurethane composite graphene is prepared by the following steps: step A1, acetonitrile and 2-bromo-5-nitropyridine are added into a three-neck flask provided with a thermometer and a stirrer, argon is introduced for 15min, 1-ethoxyvinyl-tributylstannane and bis (triphenylphosphine) palladium dichloride are added and stirred for 16h at 80 ℃, saturated potassium fluoride solution is added in a cooling way, an organic layer is obtained by separating liquid, an aqueous layer is extracted three times by ethyl acetate, the organic phase is combined and dried by a 4A molecular sieve, reduced pressure distillation is carried out after filtration, and the mixture is placed in a drying box and dried for 1h at 80 ℃ in vacuum, thus obtaining an intermediate product 1; Step A2, adding the intermediate product 1, tetrahydrofuran, hydrochloric acid and 4-tert-butyl catechol into a single-neck flask provided with a stirrer, reacting for 12 hours, adding saturated sodium bicarbonate solution, separating to obtain an organic layer, extracting an aqueous layer with ethyl acetate for 5 times, combining the organic phases, drying the organic phase with a 4A molecular sieve, filtering, heating and concentrating, and carrying out column chromatography with a mixed solvent of n-hexane/ethyl acetate to obtain an intermediate product 2; step A3, adding sodium hydroxide and absolute ethyl alcohol into a double-neck flask provided with a thermometer and a stirrer, stirring for 5-10min, adding an intermediate product 2, stirring for 5-10min, adding terephthalaldehyde, stirring for 30min, transferring into an ice bath kettle, dropwise adding ammonia water, reacting for 48h, adding a saturated ammonium chloride solution, separating to obtain an organic layer, extracting a water layer with dichloromethane, drying the combined organic phase with anhydrous sodium sulfate, filtering, and performing column chromatography with a dichloromethane/methanol mixed solvent to obtain an intermediate product 3; Step A4, adding sodium sulfide, an intermediate product 3 and deionized water into a small stainless steel reaction kettle, placing a rotor for sealing, stirring and reacting for 8 hours at the temperature of 0.1MPa and 100 ℃, cooling after the reaction is finished, filtering a p