CN108493494B - Electrolyte for prolonging service life of lead-acid storage battery and preparation method thereof - Google Patents
Electrolyte for prolonging service life of lead-acid storage battery and preparation method thereof Download PDFInfo
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- CN108493494B CN108493494B CN201810383016.3A CN201810383016A CN108493494B CN 108493494 B CN108493494 B CN 108493494B CN 201810383016 A CN201810383016 A CN 201810383016A CN 108493494 B CN108493494 B CN 108493494B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides an electrolyte for prolonging the service life of a lead-acid storage battery and a preparation method thereof, and relates to the technical field of lead-acid storage batteries, wherein the electrolyte for the lead-acid storage battery is compounded by a barrier liquid and a base liquid, and the barrier liquid comprises the following raw materials: epoxy modified polyethylene resin, alumina, xylene, the base fluid includes with the unloading: amino resin liquid, polysiloxane surfactant, platinum nanoparticles, polyvinylpyrrolidone, sulfuric acid and water, wherein the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid in the electrolyte for the lead-acid storage battery is 1-2: 1; the preparation method of the electrolyte for the lead-acid storage battery comprises the following steps: s1, preparing a barrier liquid; s2, preparing base liquid; s3, assembling process. The electrolyte provided by the invention has the advantages of low cost, simple assembly operation, long service life, less electrolyte loss, low maintenance cost and simple assembly method.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to an electrolyte for a lead-acid storage battery and a preparation method thereof.
Background
The lead-acid storage battery has the advantages of good reversibility, stable voltage characteristic, capability of discharging large current, low production cost, wide application range and the like, is widely applied to the fields of transportation, communication, electric power, railways, mines, ports, national defense, computers, scientific research and the like, and is one of important products in social production and operation activities and human life. However, the lead-acid storage battery currently used in production still has certain disadvantages, for example, the maintenance cost of the lead-acid storage battery is high, the amount of electrolyte in the lead-acid storage battery can be reduced after the lead-acid storage battery is used for a period of time, and even the phenomenon of drying up occurs, and the reduction of the electrolyte can directly lead to the reduction of the battery capacity, which affects the service life of the lead-acid storage battery, so that the lead-acid storage battery usually needs to be replenished with electrolyte when the electrolyte is reduced by about 20%, and this undoubtedly increases the maintenance cost of the lead-acid storage battery. The main reasons for drying are as follows: 1. the water used in the preparation of the lead-acid storage battery electrolyte has low purity, and contains a certain amount of metal ions such as copper, iron, nickel and the like, and the metal ions can reduce the hydrogen evolution potential of negative hydrogen in the use process of the lead-acid storage battery, so that the electrolysis of the water in the electrolyte is accelerated; 2. under the condition of overcharge of the lead-acid storage battery, water in the electrolyte can be hydrolyzed to generate hydrogen and oxygen, and the hydrogen and the oxygen overflow the electrolyte, so that the quality of the electrolyte is reduced; 3. the equipment failure results in an output voltage higher than the design specified voltage, and after the battery is charged, the high voltage still generates a large charging current for the battery, and the electric energy is almost completely used for water electrolysis, so that the quality reduction of the electrolyte is accelerated. In conclusion, the reason for reducing and even drying the electrolyte is mainly that water in the electrolyte is electrolyzed, and generated hydrogen and oxygen overflow, so that the reduction of the electrolyte is caused, the service life of the lead-acid storage battery is influenced, and the maintenance difficulty and cost are increased. In order to solve the problem of difficult maintenance of the common lead-acid storage battery, the maintenance-free lead-acid storage battery is produced at the same time, but the production difficulty and the production cost of the conventional maintenance-free lead-acid storage battery are far higher than those of the common lead-acid storage battery. Based on the statement, the invention provides the electrolyte for the lead-acid storage battery and the preparation method thereof, wherein the electrolyte has the advantages of low production cost, less electrolyte loss and long service life.
Disclosure of Invention
The invention aims to solve the problems of short service life, large electrolyte loss, large maintenance difficulty and high production cost in the prior art, and provides an electrolyte for a lead-acid storage battery and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the electrolyte for prolonging the service life of the lead-acid storage battery is formed by compounding a barrier liquid and a base liquid, wherein the barrier liquid comprises the following raw materials in parts by weight: 90-110 parts of epoxy modified polyethylene resin, 0.05-0.15 part of aluminum oxide and 30-40 parts of dimethylbenzene, wherein the base liquid comprises the following raw materials: 90-110 parts of amino resin liquid, 210-230 parts of polysiloxane surfactant, 8-12 parts of platinum nanoparticles, 25-35 parts of polyvinylpyrrolidone, 5000-5200 parts of sulfuric acid and 12950-13050 parts of water, wherein the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid in the electrolyte for the lead-acid storage battery is (1-2): 1.
preferably, the barrier liquid comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyethylene resin, 0.1 part of alumina and 35 parts of xylene.
Preferably, the base solution comprises the following raw materials in parts by weight: 100 parts of amino resin liquid, 220 parts of polysiloxane surfactant, 10 parts of platinum nanoparticles, 30 parts of polyvinylpyrrolidone, 5100 parts of sulfuric acid and 13000 parts of water.
Preferably, the epoxy modified polyethylene resin is prepared by the following method, which comprises the following specific steps: firstly plasticating the polyethylene resin, then extruding, hot-pressing and cutting the plasticated polyethylene resin, the epoxy resin and the curing agent in a double-screw extruder to obtain the epoxy modified polyethylene resin.
Preferably, the epoxy resin content in the epoxy modified polyethylene resin is 10% to 15%.
The invention also provides a preparation method of the electrolyte for the lead-acid storage battery, which comprises the following steps:
s1, preparation of a barrier liquid: weighing epoxy modified polyethylene resin, alumina and xylene, heating and dissolving the epoxy modified polyethylene resin in the xylene, keeping the temperature unchanged, and adding the alumina for dispersion to obtain a barrier liquid for later use;
s2, preparation of base liquid: weighing amino resin liquid, polysiloxane surfactant, platinum nanoparticles, polyvinylpyrrolidone, sulfuric acid and water, preparing the weighed sulfuric acid and water into sulfuric acid solution, adding the polysiloxane surfactant and the polyvinylpyrrolidone into the sulfuric acid solution, continuously stirring the mixture until the mixture is uniform to obtain a mixture, and adding the weighed amino resin liquid and the platinum nanoparticles into the mixture to be uniformly dispersed to obtain base liquid;
s3, assembly process: adding the base liquid prepared in the step S2 into a lead-acid storage battery shell, and then according to the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid of 1-2: 1, calculating the adding mass of the barrier liquid, weighing the barrier liquid prepared in the step S1 according to the calculated adding mass of the barrier liquid, adding the barrier liquid above the base liquid of the lead-acid storage battery, and then performing charging operation until a barrier film is formed on the surface of the base liquid, thus finishing the assembly of the electrolyte for the lead-acid storage battery.
Preferably, the dispersing method is any one of ultrasonic dispersion or oscillation dispersion, and the conditions of ultrasonic dispersion are as follows: the ultrasonic frequency is 25KHz, the ultrasonic time is 30min, the ultrasonic temperature is 45 ℃, and the oscillation dispersion conditions are as follows: the oscillation amplitude is 20mm, the oscillation time is 50min, and the oscillation temperature is 45 ℃.
The invention provides an electrolyte for prolonging the service life of a lead-acid storage battery, which has the advantages compared with the prior art that:
the electrolyte provided by the invention is particularly suitable for the technical field of lead-acid storage batteries, platinum nanoparticles are added into a conventional sulfuric acid aqueous solution, hydrogen and oxygen generated by water electrolysis in the electrolyte can be converted into water through a combination reaction, the water consumed by electrolysis is converted into the original liquid water state, the platinum nanoparticles originally positioned at the bottom of the base solution can be suspended in the base solution by adding the surface activity of polysiloxane, the contact area of the platinum nanoparticles with the hydrogen and the oxygen is increased, the overflow of the hydrogen and the oxygen is reduced, meanwhile, the polysiloxane surfactant can be adsorbed on the surface of a polar plate to form a protective layer on the surface of the polar plate, the formation of lead sulfate precipitates is reduced, the precipitation of hydrogen on a negative polar plate is inhibited, the electrolytic reaction of water is inhibited, and the polysiloxane surfactant can promote the amino resin liquid suspended in the base solution to be layered with the water in the base solution in the electrolyte composition charging process, the invention is beneficial to the rapid crosslinking reaction between the amino in the amino resin liquid in the base liquid and the hydroxyl in the epoxy modified polyethylene resin under the action of the alumina to generate a barrier film with excellent elasticity and gas barrier property, can reduce the reaction between the outside air entering the electrolyte base liquid and the generated hydrogen, and can ensure that the hydrogen and the oxygen which are not reacted in time still exist in the base liquid, so as to promote the hydrogen and the oxygen which are reacted in the base liquid to be converted into water under the action of the platinum nano catalyst, further reduce the loss amount of the water in the electrolyte and prolong the service life of the lead-acid storage battery, in addition, the invention also provides a preparation method of the electrolyte for prolonging the service life of the lead-acid storage battery, the epoxy modified polyethylene resin is heated and dissolved in the xylene, and the temperature is kept unchanged so as to ensure the solubility of the epoxy modified polyethylene resin in the xylene, the obtained barrier liquid has excellent fluidity, the smooth operation of adding the barrier liquid on the base liquid is ensured, the electrolyte needs to be charged after the base liquid and the barrier liquid are assembled, the generated heat can accelerate the water stratification of the amino resin liquid and the base liquid in the charging process, the contact area of the amino resin liquid and the epoxy modified polyethylene resin is further increased, the generation of a barrier film on the upper surface of the base liquid is accelerated, and the assembling time of the electrolyte is shortened on the premise of ensuring the performance of the electrolyte. Compared with a maintenance-free lead-acid storage battery, the electrolyte disclosed by the invention is low in cost, simple in assembly and operation and similar in performance, and compared with a common lead-acid storage battery, the electrolyte disclosed by the invention is long in service life, less in electrolyte loss and low in maintenance cost.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
The invention provides an electrolyte for prolonging the service life of a lead-acid storage battery, which is formed by compounding a barrier liquid and a base liquid, wherein the barrier liquid comprises the following raw materials in parts by weight: 90 parts of epoxy modified polyethylene resin, 0.05 part of alumina and 30 parts of xylene, wherein the base liquid comprises the following raw materials: 90 parts of amino resin liquid, 210 parts of polysiloxane surfactant, 8 parts of platinum nanoparticles, 25 parts of polyvinylpyrrolidone, 5000 parts of sulfuric acid and 12950 parts of water, wherein the mass ratio of epoxy modified polyethylene resin to amino resin liquid in the electrolyte for the lead-acid storage battery is (2): 1, the content of epoxy resin in the epoxy modified polyethylene resin is 10 percent;
the assembly method comprises the following steps:
s1, preparation of a barrier liquid: weighing epoxy modified polyethylene resin, alumina and xylene, heating and dissolving the epoxy modified polyethylene resin in the xylene, keeping the temperature unchanged, and adding the alumina for dispersion to obtain a barrier liquid for later use;
s2, preparation of base liquid: weighing amino resin liquid, polysiloxane surfactant, platinum nanoparticles, polyvinylpyrrolidone, sulfuric acid and water, preparing the weighed sulfuric acid and water into sulfuric acid solution, adding the polysiloxane surfactant and the polyvinylpyrrolidone into the sulfuric acid solution, continuously stirring until the mixture is uniform to obtain a mixture, adding the weighed amino resin liquid and the platinum nanoparticles into the mixture, transferring the mixture into an ultrasonic instrument with the ultrasonic frequency of 25KHz, the ultrasonic time of 30min and the ultrasonic temperature of 45 ℃ for ultrasonic dispersion, and obtaining base liquid after the mixture is uniformly dispersed;
s3, assembly process: adding the base solution prepared in the step S2 into a lead-acid storage battery shell, and then according to the mass ratio of the epoxy modified polyethylene resin to the amino resin solution of 2: 1, calculating the adding mass of the barrier liquid, weighing the barrier liquid prepared in the step S1 according to the calculated adding mass of the barrier liquid, adding the barrier liquid above the base liquid of the lead-acid storage battery, and then performing charging operation until a barrier film is formed on the surface of the base liquid, thus finishing the assembly of the electrolyte for the lead-acid storage battery.
Example 2
The invention provides an electrolyte for prolonging the service life of a lead-acid storage battery, which is formed by compounding a barrier liquid and a base liquid, wherein the barrier liquid comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyethylene resin, 0.1 part of alumina and 35 parts of xylene, wherein the base liquid comprises the following raw materials: 100 parts of amino resin liquid, 220 parts of polysiloxane surfactant, 10 parts of platinum nanoparticles, 30 parts of polyvinylpyrrolidone, 5100 parts of sulfuric acid and 13000 parts of water, wherein the mass ratio of epoxy modified polyethylene resin to amino resin liquid in the electrolyte for the lead-acid storage battery is 1.5: 1, the content of epoxy resin in the epoxy modified polyethylene resin is 13 percent;
the assembly method comprises the following steps:
s1, preparation of a barrier liquid: weighing epoxy modified polyethylene resin, alumina and xylene, heating and dissolving the epoxy modified polyethylene resin in the xylene, keeping the temperature unchanged, and adding the alumina for dispersion to obtain a barrier liquid for later use;
s2, preparation of base liquid: weighing amino resin liquid, polysiloxane surfactant, platinum nanoparticles, polyvinylpyrrolidone, sulfuric acid and water, preparing the weighed sulfuric acid and water into sulfuric acid solution, adding the polysiloxane surfactant and the polyvinylpyrrolidone into the sulfuric acid solution, continuously stirring until the mixture is uniform to obtain a mixture, adding the weighed amino resin liquid and the platinum nanoparticles into the mixture, transferring the mixture into an ultrasonic instrument with the ultrasonic frequency of 25KHz, the ultrasonic time of 30min and the ultrasonic temperature of 45 ℃ for ultrasonic dispersion, and obtaining base liquid after the mixture is uniformly dispersed;
s3, assembly process: adding the base solution prepared in the step S2 into a lead-acid storage battery shell, and then according to the mass ratio of the epoxy modified polyethylene resin to the amino resin solution of 1.5: 1, calculating the adding mass of the barrier liquid, weighing the barrier liquid prepared in the step S1 according to the calculated adding mass of the barrier liquid, adding the barrier liquid above the base liquid of the lead-acid storage battery, and then performing charging operation until a barrier film is formed on the surface of the base liquid, thus finishing the assembly of the electrolyte for the lead-acid storage battery.
Example 3
The invention provides an electrolyte for prolonging the service life of a lead-acid storage battery, which is formed by compounding a barrier liquid and a base liquid, wherein the barrier liquid comprises the following raw materials in parts by weight: 110 parts of epoxy modified polyethylene resin, 0.15 part of alumina and 40 parts of xylene, wherein the base liquid comprises the following raw materials: 110 parts of amino resin liquid, 230 parts of polysiloxane surfactant, 12 parts of platinum nanoparticles, 35 parts of polyvinylpyrrolidone, 5200 parts of sulfuric acid and 13050 parts of water, wherein the mass ratio of epoxy modified polyethylene resin to amino resin liquid in the electrolyte for the lead-acid storage battery is 1: 1, the content of epoxy resin in the epoxy modified polyethylene resin is 15 percent;
the assembly method comprises the following steps:
s1, preparation of a barrier liquid: weighing epoxy modified polyethylene resin, alumina and xylene, heating and dissolving the epoxy modified polyethylene resin in the xylene, keeping the temperature unchanged, and adding the alumina for dispersion to obtain a barrier liquid for later use;
s2, preparation of base liquid: weighing amino resin liquid, polysiloxane surfactant, platinum nanoparticles, polyvinylpyrrolidone, sulfuric acid and water, preparing the weighed sulfuric acid and water into sulfuric acid solution, adding the polysiloxane surfactant and the polyvinylpyrrolidone into the sulfuric acid solution, continuously stirring until the mixture is uniform to obtain a mixture, adding the weighed amino resin liquid and the platinum nanoparticles into the mixture, transferring the mixture into an ultrasonic instrument with the ultrasonic frequency of 25KHz, the ultrasonic time of 30min and the ultrasonic temperature of 45 ℃ for ultrasonic dispersion, and obtaining base liquid after the mixture is uniformly dispersed;
s3, assembly process: adding the base solution prepared in the step S2 into a lead-acid storage battery shell, and then, according to the mass ratio of the epoxy modified polyethylene resin to the amino resin solution of 1: 1, calculating the adding mass of the barrier liquid, weighing the barrier liquid prepared in the step S1 according to the calculated adding mass of the barrier liquid, adding the barrier liquid above the base liquid of the lead-acid storage battery, and then performing charging operation until a barrier film is formed on the surface of the base liquid, thus finishing the assembly of the electrolyte for the lead-acid storage battery.
In each of examples 1 to 3, the epoxy-modified polyethylene resin was prepared by the following method: firstly plasticating the polyethylene resin, then extruding, hot-pressing and cutting the plasticated polyethylene resin, the epoxy resin and the curing agent in a double-screw extruder to obtain the epoxy modified polyethylene resin.
The electrolyte and the preparation method in the embodiments 1 to 3 are combined with a production process of a common lead-acid storage battery to respectively produce the lead-acid storage battery, the capacity of the lead-acid storage battery is detected, a commercially available common lead-acid storage battery and a commercially available maintenance-free lead-acid storage battery which are matched with the detected battery capacity are selected to respectively carry out a charge-discharge cycle experiment, in the charge-discharge cycle process, a voltage which is 20% higher than a specified voltage is continuously input into the lead-acid storage battery, the reduction rate of the capacity of the lead-acid storage battery and the reduction rate of the electrolyte after 400 cycles are calculated, and the result is shown.
Table 1:
| detecting items | Capacity reduction rate% | Reduction ratio of electrolyte% |
| Example 1 | 35.1 | 8.8 |
| Example 2 | 34.8 | 8.1 |
| Example 3 | 35.6 | 9.1 |
| Ordinary lead-acid accumulator | 72.6 | 24.7 |
| Maintenance-free lead-acid storage battery | 33.7 | 7.6 |
The experimental results in table 1 show that after the lead-acid storage battery obtained in examples 1 to 3 is cycled for 400 times under the condition of 20% of overvoltage, the battery capacity reduction rate and the electrolyte reduction rate are both similar to those of a maintenance-free lead-acid storage battery, and the capacity reduction rate and the electrolyte reduction rate of the lead-acid storage battery obtained in examples 1 to 3 and the maintenance-free lead-acid storage battery are both obviously lower than those of a common lead-acid storage battery, so that the lead-acid storage battery electrolyte provided by the invention can effectively solve the problem of large electrolyte loss of the common lead-acid storage battery, and further prolongs the service life of the lead-acid; the production of the lead-acid storage battery can be completed only by preparing the barrier liquid and the base liquid and matching the barrier liquid and the base liquid and combining the production process of the common lead-acid storage battery, and compared with the commercially available maintenance-free lead-acid storage battery, the production method has the advantages of simpler operation, low production cost and obviously reduced maintenance difficulty.
Comparative example 1
The barrier liquid component in the electrolyte formulation of example 2 was removed, and the amino resin liquid in the base liquid was removed, under the same conditions as in example 2.
The lead-acid storage battery is produced by using the electrolyte formula and the preparation method of the comparative example 1 and combining the production process of the common lead-acid storage battery, a charge-discharge cycle experiment is carried out on the produced lead-acid storage battery, in the charge-discharge cycle process, a voltage which is 20% higher than the specified voltage is continuously input into the lead-acid storage battery, and the reduction rate of the capacity of the lead-acid storage battery and the reduction rate of the electrolyte after 400 cycles are calculated, and the results are shown in table 2.
Table 2:
| detecting items | Capacity reduction rate% | Reduction ratio of electrolyte% |
| Comparative example 1 | 60.3 | 19.1 |
Compared with the test results in the table 1, the test results in the table 2 show that compared with the common lead-acid storage battery, the capacity reduction rate and the electrolyte reduction rate in the comparative example 1 are reduced, but the reduction range is far smaller than that in the examples 1-3 and the maintenance-free lead-acid storage battery, so that the barrier film formed by the barrier liquid and the amino resin liquid in the formula of the invention plays an important role in the service life of the electrolyte of the lead-acid storage battery and the reduction of the electrolyte.
In examples 4 to 15, the mass ratio of the epoxy-modified polyethylene resin and the amino resin liquid in example 2 was changed to the mass ratio shown in table 3 without changing the total mass of the epoxy-modified polyethylene resin and the amino resin liquid, and the film forming time in example 2 and examples 4 to 15 was recorded under the same conditions as in example 2, and the barrier films located above the base liquid obtained in examples 2 and 4 to 15 were taken out and the performance was measured, and the results are shown in table 3.
Table 3:
in Table 1, 1) A/B is the mass ratio of epoxy modified polyethylene resin to amino resin liquid; 2) elongation was measured according to GBB022-91 standard; 3) the shrinkage rate is detected by an RSY-03 heat shrinkage tester according to the GB/T13519-; 4) the air permeability is measured by a pressure difference method by adopting a GB/T1038-2000 standard, and the corresponding air permeability is measured within 24 hours.
The results in table 3 show that the relationship between the ratio of the epoxy modified polyethylene resin and the amino resin liquid directly affects the film formation time of the barrier film and the performance of the barrier film.
With the increase of the proportion of the epoxy modified polyethylene resin, the film forming time is gradually reduced, and when the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid exceeds 1.5: 1, gradually prolonging the film forming time, and when the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid exceeds 2: the film forming time is obviously prolonged after 1, which shows that the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid is 1-2: 1, the film forming effect is better, and the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid is 1.5: the film forming effect is best when 1 hour; with the increase of the proportion of the epoxy modified polyethylene resin, the transverse elongation, the longitudinal elongation and the shrinkage of the barrier film gradually increase, but the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid exceeds 1: no significant change after 1; and the improvement of transverse elongation, longitudinal elongation and shrinkage rate can make the barrier film in the lead-acid storage battery use process, along with rocking, the contact part of the barrier film and the lead-acid storage battery shell is subjected to telescopic change, the phenomenon that the barrier film is broken in the rocking process is prevented, the barrier time of the barrier film is further prolonged, and the service life of the electrolyte for the lead-acid storage battery is prolonged.
With the increase of the proportion of the epoxy modified polyethylene resin, the permeation amount of hydrogen and oxygen is increased, and when the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid exceeds 2: after 1, the permeation amount of hydrogen and oxygen is obviously increased, which shows that the electrolyte obtained by the embodiment of the invention has small air permeability, can effectively prevent the hydrogen and oxygen generated by electrolysis of water in the electrolyte from overflowing, and simultaneously prevents external air from entering the electrolyte to perform chemical reaction with the hydrogen in the base liquid.
The data in table 1 show that the combined effect of example 2 is the best, so the mass ratio of epoxy modified polyethylene resin to amino resin liquid is 1.5: the film forming effect of the barrier film is best at 1 time.
Examples 16 to 21 were carried out by replacing the epoxy-modified polyethylene resin in the formulation of example 2 with epoxy-modified polyethylene resins having epoxy resin contents of 5%, 8%, 10%, 15%, 18% and 20% in an equal amount, and the electrolyte solutions obtained in the same manner as in example 2 were successively subjected to performance tests while taking out the barrier films located above the base solutions obtained in examples 16 to 21, and the results are shown in table 4.
Table 4:
in Table 4, a) elongation was measured according to GBB022-91 standard; b) the shrinkage rate is detected by an RSY-03 heat shrinkage tester according to the GB/T13519-; c) the air permeability is measured by a pressure difference method by adopting a GB/T1038-2000 standard, and the corresponding air permeability is measured within 24 hours.
The results in Table 4 show that the film forming time is gradually reduced with the increase of the content of the epoxy resin in the epoxy-modified polyethylene resin, the film forming time is gradually prolonged when the content of the epoxy resin in the epoxy-modified polyethylene resin exceeds 15%, the film forming time is shorter when the content of the epoxy resin in the epoxy-modified polyethylene resin is 10% to 15%, and the transverse elongation, the longitudinal elongation and the shrinkage rate are increased with the increase of the content of the epoxy resin in the epoxy-modified polyethylene resin, but the change is not obvious, particularly, the change is more slight when the content of the epoxy resin in the epoxy-modified polyethylene resin exceeds 15%, which indicates that the reaction between the hydroxyl group in the epoxy resin and the amino group in the amino resin liquid in the base liquid can be accelerated with the increase of the content of the epoxy resin in the epoxy-modified polyethylene resin, and the reaction is inhibited when the content of the epoxy resin is increased to a certain extent, and the increase of the content of the epoxy resin in the epoxy modified polyethylene resin can improve the transverse expansion rate, the longitudinal expansion rate and the shrinkage rate of the barrier film, but the improvement rate of the performance of the barrier film is small after the content of the epoxy resin exceeds 15 percent, and the cost performance is high when the content of the epoxy resin in the epoxy modified polyethylene resin is 10 to 15 percent in comprehensive consideration.
The dispersion method in example 2 was changed to oscillatory dispersion under the following conditions: the oscillation amplitude is 20mm, the oscillation time is 50min, the oscillation temperature is 45 ℃, other conditions are the same as example 2, a voltage higher than a specified voltage by 20% is continuously input into the obtained lead-acid storage battery, and the reduction rate of the capacity of the lead-acid storage battery and the reduction rate of the electrolyte after 400 cycles are calculated, so that the result is similar to the result obtained in example 2, and the result shows that the performance of the electrolyte obtained by dispersing the amino resin liquid and the platinum nanoparticles into the mixture by using an ultrasonic dispersion or oscillation dispersion method is consistent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. The electrolyte for improving the service life of the lead-acid storage battery is characterized by being formed by compounding a barrier liquid and a base liquid, wherein the barrier liquid comprises the following raw materials in parts by weight: 90-110 parts of epoxy modified polyethylene resin, 0.05-0.15 part of aluminum oxide and 30-40 parts of dimethylbenzene, wherein the base liquid comprises the following raw materials: 90-110 parts of amino resin liquid, 210-230 parts of polysiloxane surfactant, 8-12 parts of platinum nanoparticles, 25-35 parts of polyvinylpyrrolidone, 5000-5200 parts of sulfuric acid and 12950-13050 parts of water, wherein the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid in the electrolyte for the lead-acid storage battery is (1-2): 1;
the epoxy modified polyethylene resin is prepared by the following method, and the specific operation is as follows: firstly plasticating the polyethylene resin, then extruding, hot-pressing and cutting the plasticated polyethylene resin, the epoxy resin and the curing agent in a double-screw extruder to obtain the epoxy modified polyethylene resin.
2. The electrolyte for prolonging the service life of a lead-acid storage battery according to claim 1, wherein the barrier liquid comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyethylene resin, 0.1 part of alumina and 35 parts of xylene.
3. The electrolyte for prolonging the service life of a lead-acid storage battery according to claim 1, wherein the base solution comprises the following raw materials in parts by weight: 100 parts of amino resin liquid, 220 parts of polysiloxane surfactant, 10 parts of platinum nanoparticles, 30 parts of polyvinylpyrrolidone, 5100 parts of sulfuric acid and 13000 parts of water.
4. The electrolyte for improving the service life of the lead-acid storage battery according to claim 1 or 2, wherein the epoxy resin content in the epoxy modified polyethylene resin is 10-15%.
5. A method for preparing electrolyte for prolonging the service life of a lead-acid storage battery is characterized by comprising the following steps:
s1, preparation of a barrier liquid: weighing epoxy modified polyethylene resin, alumina and xylene, heating and dissolving the epoxy modified polyethylene resin in the xylene, keeping the temperature unchanged, and adding the alumina for dispersion to obtain a barrier liquid for later use;
s2, preparation of base liquid: weighing amino resin liquid, polysiloxane surfactant, platinum nanoparticles, polyvinylpyrrolidone, sulfuric acid and water, preparing the weighed sulfuric acid and water into sulfuric acid solution, adding the polysiloxane surfactant and the polyvinylpyrrolidone into the sulfuric acid solution, continuously stirring the mixture until the mixture is uniform to obtain a mixture, and adding the weighed amino resin liquid and the platinum nanoparticles into the mixture to be uniformly dispersed to obtain base liquid;
s3, assembly process: adding the base liquid prepared in the step S2 into a lead-acid storage battery shell, and then according to the mass ratio of the epoxy modified polyethylene resin to the amino resin liquid of 1-2: 1, calculating the adding mass of the barrier liquid, weighing the barrier liquid prepared in the step S1 according to the calculated adding mass of the barrier liquid, adding the barrier liquid above the base liquid of the lead-acid storage battery, and then performing charging operation until a barrier film is formed on the surface of the base liquid, namely completing the assembly of the electrolyte for the lead-acid storage battery;
the epoxy modified polyethylene resin is prepared by the following method, and the specific operation is as follows: firstly plasticating the polyethylene resin, then extruding, hot-pressing and cutting the plasticated polyethylene resin, the epoxy resin and the curing agent in a double-screw extruder to obtain the epoxy modified polyethylene resin.
6. The method for preparing the electrolyte for prolonging the service life of the lead-acid storage battery according to claim 5, wherein the dispersing method is any one of ultrasonic dispersion or oscillation dispersion, and the conditions of ultrasonic dispersion are as follows: the ultrasonic frequency is 25KHz, the ultrasonic time is 30min, the ultrasonic temperature is 45 ℃, and the oscillation dispersion conditions are as follows: the oscillation amplitude is 20mm, the oscillation time is 50min, and the oscillation temperature is 45 ℃.
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