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CN-122025849-A - Lead-acid storage battery based on composite electrolyte and preparation method thereof

CN122025849ACN 122025849 ACN122025849 ACN 122025849ACN-122025849-A

Abstract

The invention discloses a lead-acid storage battery based on composite electrolyte and a preparation method thereof, in particular relates to the technical field of materials, and relates to a lead-acid storage battery based on composite electrolyte and a preparation method thereof; the lead-acid storage battery based on the composite electrolyte is prepared from vinyl imidazole, 1, 3-propane sultone, azodiisobutyronitrile, concentrated sulfuric acid, nano silicon dioxide and niobium pentoxide, and utilizes the strong interaction between sulfonic acid groups on an acidic ionic liquid polymer chain and the surface of nano metal oxide to anchor a large amount of corrosive hydrogen ions and sulfate ions on a stable polymer-inorganic framework in situ, so that the concentration of free and movable strong corrosive components in the electrolyte is greatly reduced, and the electrochemical corrosion power of the electrolyte is weakened.

Inventors

  • WANG CHAO
  • SUN GANG
  • LU DEZHI
  • ZHANG YONGQIANG
  • GUAN ZHONGYANG

Assignees

  • 山东久力新能源集团有限公司

Dates

Publication Date
20260512
Application Date
20260206

Claims (10)

  1. 1. The preparation method of the lead-acid storage battery based on the composite electrolyte is characterized by comprising the following steps of: S1, placing vinyl imidazole monomer and 1, 3-propane sultone into a Schlank tube, carrying out oil bath reaction for 10 hours under the condition of argon environment at the temperature of 55 ℃ and the stirring speed of 300r/min, repeatedly washing for three times by using anhydrous diethyl ether, and then drying for 6 hours under the condition of 50 ℃ to obtain zwitterionic ionic liquid; S2, dissolving the zwitterionic ionic liquid obtained in the step S1 in an anhydrous acetonitrile solvent, adding azodiisobutyronitrile, carrying out polymerization reaction for 6 hours under the reflux condensation condition at the temperature of 65 ℃ in a nitrogen environment, dropwise adding the product solution into excessive anhydrous diethyl ether for sedimentation, filtering and separating the obtained polymer solid, washing the polymer solid with diethyl ether again, drying the polymer solid to constant weight under the vacuum condition at the temperature of 60 ℃, mixing the polymer solid with concentrated sulfuric acid, and carrying out mechanical stirring for 3 hours under the condition of the stirring speed of 400r/min at the temperature of 35 ℃ to obtain an acidic ionic liquid polymer; S3, mixing nano silicon dioxide and niobium pentoxide, placing the mixture into a nitric acid solution with 3 times of volume, stirring the mixture at a constant temperature of 80 ℃ for 2 hours, washing the mixture to be neutral by deionized water, drying the mixture at 20 ℃, dispersing the mixture into an ethanol solution with 3 times of volume and containing a silane coupling agent, carrying out ultrasonic treatment for 30 minutes, carrying out reflux stirring for 4 hours at a temperature of 70 ℃, and carrying out centrifugal separation, ethanol washing and drying to obtain the surface-modified active metal oxide; S4, mixing the acidic ionic liquid polymer obtained in the step S2 with the surface-modified active metal oxide obtained in the step S3, transferring into a high-speed shearing emulsifying machine, continuously homogenizing for 1h at the temperature of 50 ℃ at the rotating speed of 3000r/min, and then placing the slurry into a die, and curing for 24h at the temperature of 70 ℃ to obtain the composite electrolyte; S5, preparing a lead-calcium alloy grid according to a conventional process, coating lead paste to form positive and negative polar plates, stacking the polar plates and the diaphragm in a staggered manner, loading the positive and negative polar plates and the diaphragm into a battery shell, crushing the electrolyte material obtained in the S4 to 8-12 mu m powder, drying the powder until the water content is lower than 0.5%, adding the powder into sulfuric acid solution according to the content of 10%, injecting the sulfuric acid solution into the shell, sealing a battery cover plate by adopting a heat sealing process, and then applying an initialization process to obtain the lead-acid storage battery based on the composite electrolyte.
  2. 2. The method for preparing the lead-acid storage battery based on the composite electrolyte according to claim 1, wherein the lead-acid storage battery based on the composite electrolyte comprises the following raw materials in parts by weight: 0.753 to 1.882 parts of vinyl imidazole, 0.977 to 2.443 parts of 1, 3-propane sultone, 0.017 to 0.043 parts of azodiisobutyronitrile, 1.730 to 4.325 parts of concentrated sulfuric acid, 0.461 to 1.362 parts of nano silicon dioxide and 0.454 to 1.874 parts of niobium pentoxide.
  3. 3. The method for preparing the lead-acid storage battery based on the composite electrolyte according to claim 1, wherein the zwitterionic ionic liquid in the S2 is dissolved in an anhydrous acetonitrile solvent to prepare a solution with the concentration of 20wt.%.
  4. 4. The method for preparing the lead-acid storage battery based on the composite electrolyte according to claim 1, wherein the concentrated sulfuric acid in the S2 is 98% by mass.
  5. 5. The method for preparing a lead-acid storage battery based on composite electrolyte according to claim 1, wherein the mass fraction of the nitric acid solution in the S3 is 10wt.%.
  6. 6. The method for preparing a lead-acid storage battery based on composite electrolyte according to claim 1, wherein the ethanol solution containing the silane coupling agent in S3 specifically contains 1% of the silane coupling agent.
  7. 7. The method for preparing a lead-acid battery based on composite electrolyte according to claim 1, wherein the density of the sulfuric acid solution in S5 is 1.28g/ml.
  8. 8. The method for preparing the lead-acid storage battery based on the composite electrolyte according to claim 1, wherein the volume of the sulfuric acid solution in the step S5 is 60% of the using amount of the electrolyte.
  9. 9. The method for preparing the lead-acid storage battery based on the composite electrolyte according to claim 1, wherein the initialization forming process is characterized in that the lead-acid storage battery is firstly charged for 24 hours with small current constant current with the rate of 0.05 percent, then is kept stand for 2 hours, and is charged and discharged for 3 times with current of 0.1 percent, and each cycle comprises charging for 10 hours and discharging to a final voltage of 1.75V.
  10. 10. A composite electrolyte-based lead acid battery prepared according to the preparation method of any one of claims 1 to 9.

Description

Lead-acid storage battery based on composite electrolyte and preparation method thereof Technical Field The invention relates to the technical field of materials, in particular to a lead-acid storage battery based on composite electrolyte and a preparation method thereof. Background As a long-history electrochemical energy storage device, the lead-acid storage battery still occupies important positions in the fields of automobile starting, uninterrupted power supply, large-scale energy storage and the like because of mature technology, low cost and high recovery rate, so that the development of a novel lead-acid storage battery has important significance. The lead-acid accumulator includes lead alloy grid, lead plaster active matter, sulfuric acid electrolyte and diaphragm, in which the lead alloy grid is usually lead-antimony alloy or lead-calcium alloy to form electrode skeleton for supporting active matter and conducting current, the lead plaster active matter is lead plaster made of lead powder, in which the positive electrode lead plaster is formed into lead dioxide, and its negative electrode is sponge lead, and is the core material for electrochemical reaction, sulfuric acid electrolyte is dilute sulfuric acid water solution with concentration of about 30-40%, and can be used as ion conductor, and in the course of charging and discharging the current is transferred by means of migration of hydrogen ion and sulfate ion, and the diaphragm is usually glass wool for isolating positive electrode and negative electrode so as to prevent short circuit, at the same time the electrolyte is adsorbed. However, when the electrolyte is actually used, the electrolyte still has some defects, such as unsafe, easy leakage and easy volatilization of the traditional liquid sulfuric acid electrolyte, easy occurrence of electrolysis of water during overcharging, generation of hydrogen and oxygen, regular maintenance and explosion risk, serious corrosion, gradual corrosion of a positive grid in a strong acid oxidation environment to lead oxide or lead sulfate which is not conductive, separation of active substances from a current collector, increase of internal resistance and capacity attenuation of a battery, heavy salinization degree, long-term use of the traditional technology under partial charge state, recrystallization of the lead sulfate on the surface of a negative electrode to coarse and compact crystals, difficult reduction to active lead, and permanent loss of capacity of the battery. Disclosure of Invention In order to solve the problems, the invention particularly provides a lead-acid storage battery based on composite electrolyte and a preparation method thereof, which solve the problems in the prior art. In order to achieve the above purpose, the present invention provides the following technical solutions: A lead-acid storage battery based on composite electrolyte and a preparation method thereof comprise the following steps: S1, placing vinyl imidazole monomer and 1, 3-propane sultone into a Schlank tube, carrying out oil bath reaction for 10 hours under the condition of argon environment at the temperature of 55 ℃ and the stirring speed of 300r/min, repeatedly washing for three times by using anhydrous diethyl ether, and then drying for 6 hours under the condition of 50 ℃ to obtain zwitterionic ionic liquid; S2, dissolving the zwitterionic ionic liquid obtained in the step S1 in an anhydrous acetonitrile solvent, adding azodiisobutyronitrile, carrying out polymerization reaction for 6 hours under the reflux condensation condition at the temperature of 65 ℃ in a nitrogen environment, dropwise adding the product solution into excessive anhydrous diethyl ether for sedimentation, filtering and separating the obtained polymer solid, washing the polymer solid with diethyl ether again, drying the polymer solid to constant weight under the vacuum condition at the temperature of 60 ℃, mixing the polymer solid with concentrated sulfuric acid, and carrying out mechanical stirring for 3 hours under the condition of the stirring speed of 400r/min at the temperature of 35 ℃ to obtain an acidic ionic liquid polymer; S3, mixing nano silicon dioxide and niobium pentoxide, placing the mixture into a nitric acid solution with 3 times of volume, stirring the mixture at a constant temperature of 80 ℃ for 2 hours, washing the mixture to be neutral by deionized water, drying the mixture at 20 ℃, dispersing the mixture into an ethanol solution with 3 times of volume and containing a silane coupling agent, carrying out ultrasonic treatment for 30 minutes, carrying out reflux stirring for 4 hours at a temperature of 70 ℃, and carrying out centrifugal separation, ethanol washing and drying to obtain the surface-modified active metal oxide; S4, mixing the acidic ionic liquid polymer obtained in the step S2 with the surface-modified active metal oxide obtained in the step S3, transferring into a high-speed shearing emulsifying machin