KR102187662B1 - A method for manufacturing electrolytic solution of lead-acid battery to provide discharge capacity improvement and durability improvement - Google Patents

Abstract

The present invention relates to a method of manufacturing an electrolyte of a lead-acid battery for providing improved characteristics of electrolyte decrease and life. More particularly, the present invention relates to a method of manufacturing an electrolyte of a lead-acid battery for providing improved characteristics of electrolyte decrease and life, which prevents magnetic corrosion of a negative electrode and reduces the generation of hydrogen gas when an electrolyte is prepared by adding EMI-BF4, an ionic liquid, as an additive to the electrolyte of a lead-acid battery, and then added to the lead-acid battery, thereby providing a lead-acid battery with improved characteristics of electrolyte decrease, durability, and product life. According to the present invention, there is an effect of providing a lead-acid battery with improved characteristics of electrolyte decrease, durability, and product life by adding EMI-BF4, which is an ionic liquid, to prepare an electrolyte, which is then introduced into a lead-acid battery, thereby preventing magnetic corrosion of a negative electrode and reducing the generation of hydrogen gas.

Description

A method for manufacturing electrolytic solution of lead-acid battery to provide discharge capacity improvement and durability improvement.

The present invention relates to a method of manufacturing an electrolyte solution for a lead acid battery to provide improved liquid reduction characteristics and life, and more particularly, as an additive to the electrolyte solution of a lead acid battery, an electrolyte solution is prepared by adding EMI-BF ₄ which is an ionic liquid. When inserted into a lead acid battery, the lead acid battery prevents magnetic corrosion of the negative electrode and reduces the generation of hydrogen gas to provide a lead acid battery with improved liquid reduction characteristics, durability, and product life. It relates to a method of manufacturing an electrolyte.

A lead acid battery is a storage battery capable of charging and discharging by an oxidation-reduction reaction between two electrode plates made of lead and lead oxide, respectively, and sulfuric acid, an electrolyte.

This generally includes a plurality of positive and negative plates, and the negative and positive plates are alternately arranged with a separator for separating each of the plates from adjacent plates.

The spaces other than the electrode plates and separators arranged in this way are filled with sulfuric acid, an electrolyte.

Such a lead acid battery is a stable technology according to a long history of use, and has advantages of low price, high capacity, and easy recycling.

Meanwhile, a lead acid battery generally used in automobiles, etc. is a secondary battery capable of charging and discharging.

Sulfuric acid (H2SO4) is used as an electrolytic solution, lead dioxide (PbO2) is applied to the positive electrode as an active material of the electrode plate, and spongy lead (Pb) is applied to the negative electrode, and mixed to form a paste.

The thus-made active material undergoes a coating operation, which is a work applied to a substrate, and after undergoing a aging process and a drying process according to the characteristics of the positive electrode and the negative electrode, the prepared positive electrode plate and the negative electrode plate are overlapped to produce an electrode plate group.

Several of the electrode plate groups are connected in series according to the capacity of the storage battery and are accommodated in a case.

The accommodated electrode plate group undergoes a chemical conversion process, which is charged so as to have electrical properties, and thus serves as a lead acid battery.

In the case of the manufacturing method of lead acid battery and lead acid battery, which is Korean Patent Registration No. 10-1011859, which is a prior art, the molar concentration of aluminum (AL) ions was 0.01 to 0.3 mol/l, but the effect of aluminum (AL) ions was provided. It is to improve the life of lead acid batteries.

However, as the current use environment that requires lead acid batteries is becoming more and more severe, the charge/discharge characteristics of lead acid batteries are demanding products that are superior to lead acid batteries manufactured through the preceding patent documents. Shaped materials are being developed.

The recent lead acid battery industry is striving to develop a battery for micro-hybrid or mild-hybrid automobiles in environments with high charge/discharge depth, and durability that exceeds the requirements of general lead acid batteries. Is being demanded.

Therefore, there is a situation in which a new technology capable of further improving the durability is required.

Korean Patent Registration No. 10-1011859

Therefore, the present invention was devised to solve the above conventional problems,

As an additive to the electrolyte of a lead acid battery, EMI-BF ₄ , an ionic liquid, is added to prepare the electrolyte, and by injecting it into the lead acid battery, magnetic corrosion of the negative electrode is prevented, and hydrogen gas generation is reduced to reduce liquid-reduction characteristics, durability, and products. It is intended to provide a lead acid battery with improved life.

In order to achieve the problem to be solved by the present invention, a method of manufacturing an electrolyte solution for a lead acid battery for providing an improvement in liquid reduction characteristics and life according to an embodiment of the present invention,

In the process of forming a lead acid battery, in the process of introducing the secondary electrolyte,

EMI-BF ₄ additive input step (S100) in which EMI-BF ₄ , an ionic liquid of 0.08 to 0.1 wt% compared to the 1.280 kg/L specific gravity of room temperature (10 to 25°C) electrolyte (H ₂ SO ₄ ), is added as an additive. );Wow

Thereafter, by including an electrolyte solution completion step (S200) of completing the electrolyte by stirring at room temperature (10 to 25°C) for 1 to 24 hours, the problem of the present invention is solved.

Through the present inventor's method of manufacturing an electrolyte solution for a lead acid battery to provide improved liquid reduction characteristics and lifespan, an ionic liquid, EMI-BF ₄ is added to prepare an electrolyte, and the electrolyte is added to the lead acid battery to prevent magnetic corrosion of the negative electrode, There is an effect of providing a lead acid battery with improved liquid reduction characteristics, durability, and product life by reducing the generation of hydrogen gas.

1 is a process diagram showing a method of manufacturing an electrolyte solution for a lead acid battery for providing liquid reduction characteristics and life improvement according to an embodiment of the present invention.

A method of manufacturing an electrolyte solution for a lead acid battery for providing liquid reduction characteristics and life improvement according to an embodiment of the present invention,

In the process of forming a lead acid battery, in the process of introducing the secondary electrolyte,

EMI-BF ₄ additive input step (S100) in which EMI-BF ₄ , an ionic liquid of 0.08 to 0.1 wt% compared to the 1.280 kg/L specific gravity of room temperature (10 to 25°C) electrolyte (H ₂ SO ₄ ), is added as an additive. );Wow

Then, the electrolyte solution completion step (S200) of completing the electrolyte by stirring at room temperature (10 to 25°C) for 1 to 24 hours.

At this time, in the EMI-BF ₄ additive input step (S100),

Addition of an ionic liquid, EMI-BF ₄ additive, prevents self-corrosion of the cathode, and reduces the generation of hydrogen gas, thereby providing improved liquid-reducing properties and durability.

At this time, by the method of manufacturing an electrolyte solution for a lead acid battery for providing the liquid reduction characteristics and life improvement,

When the required storage capacity of the lead-acid battery is 70Ah, the storage capacity of the lead-acid battery to which the EMI-BF ₄ additive is added is a capacity of 71 to 73Ah.

At this time, by the method of manufacturing an electrolyte solution for a lead acid battery for providing the liquid reduction characteristics and life improvement,

It is possible to manufacture a lead acid battery to which an electrolyte solution containing EMI-BF ₄ additive is applied.

Hereinafter, it will be described in detail through an embodiment of a method of manufacturing an electrolyte solution for a lead acid battery for providing liquid reduction characteristics and life improvement according to the present invention.

In the case of a lead acid battery and a method of manufacturing a lead acid battery, which is a conventional Korean Patent No. 10-1011859, the molar concentration of aluminum (AL) ions was set to 0.01 to 0.3 mol/l,

By ion analysis, it is 0.3 mol/l or more, and provides only the effect of Al (aluminum) ions.

However, the method of manufacturing an electrolyte according to the present invention prevents magnetic corrosion of the negative electrode and reduces the generation of hydrogen gas by adding EMI-BF ₄ , an ionic liquid, as an additive to the electrolyte of a lead acid battery, thereby preventing liquid reduction characteristics and durability. And a lead acid battery with improved product life.

Specifically, the present invention prevents magnetic corrosion of the negative electrode and reduces hydrogen gas generation by introducing the ionic liquid EMI-BF ₄ as an additive when the secondary electrolyte is introduced during the lead acid battery formation process. It improves durability.

The following will be described in more detail the difference between the present invention and the prior art.

Currently, as the environment of performance and durability required for lead-acid batteries becomes harsh, new types of materials are being developed that meet requirements such as grid growth and corrosion inhibition, and improvement in charge/discharge characteristics of products.

The recent lead-acid battery industry is making efforts to improve the durability of batteries for customers and automotive industries who request the development of high-performance batteries in high-temperature areas, and in order to improve the durability of batteries in such environments, manufacturing with higher durability. Since technology development is required, the present invention was proposed based on this.

In the present invention, EMI-BF ₄ (1-ethyl-3-methylimidazolum tetrafluoroborate), an ionic liquid, is applied as a lead acid battery electrolyte additive to prevent self-corrosion of the negative electrode and reduce the generation of hydrogen gas to improve liquid reduction characteristics and durability. do.

Ionic liquids cannot form crystals due to the asymmetric size of cations and anions.

Among them, a substance that exists as a liquid at a temperature of 100° C. or less, or in particular, a liquid at room temperature (25° C.), unlike the characteristics of existing salts, is called an ionic liquid.

By using an ionic liquid as an additive, it was confirmed through an experiment that hydrogen gas generated during the charging and discharging process of the lead acid battery was reduced, thereby increasing the liquid reduction characteristics.

When the product is charged and discharged, H ⁺ in the electrolyte is combined with electrons generated from the cathode (Pb) to become H ₂ Gas.

However, when EMI-BF _{4 is} added, the Cationic molecules of the material are adsorbed to the cathode surface by the Van der Waals force, and combined with the generated electrons, hydrogen ions are prevented from being reduced to hydrogen gas, thereby reducing the generation of hydrogen gas. will be.

(1) Hydrogen generation process in lead acid battery

_{Pb + H 2 SO 4 → PbSO} 4 + 2H + + 2e -

(Sense is a gas _{^{fly) → H 2 - 2H + +}} 2e

(2) When EMI-BF _{4 is} added, electron transfer process

Pb + IL ⁺ →Pb(IL ⁺ )ads (*Van der waals Force)

^{Pb (IL +) ads + e} - → Pb (IL) ads

The Cationic molecule of EMI-BF4 is as follows.

The Van der Waals force is a relatively weak attraction between atoms and molecules acting at a short distance, and attraction between non-polar organic compounds.

When the EMI-BF _{4 is} not added, H+ in the electrolyte is combined with electrons generated in the cathode Pb to become H2 gas.

However, when EMI-BF _{4 is} added, the Cationic molecules of the material are adsorbed on the cathode surface by the Van der Waals force, and combined with the generated electrons, the generation of hydrogen gas is reduced.

And, BF4 ^- which is an anion part of EMI-BF ₄ (Tetrafluoroborate) is adsorbed on the surface of the negative electrode to form a film, thereby providing an effect of preventing magnetic corrosion of the negative electrode.

On the other hand, as an example of the input process, when manufacturing a lead acid battery, after completion of the chemical conversion process, the electrolyte is dumped and emptied.

Thereafter, when the liquid is changed to a secondary electrolyte (H ₂ SO ₄ ) having a specific gravity of 1.350 to 1.360 g/ml, about 0.08 to 0.1 wt% of EMI-BF ₄ is added as an additive compared to the amount of the electrolyte.

Due to the high conductivity of the ionic liquid, its special molecular structure and electron absorption, it helps to improve the life of the lead acid battery by preventing liquid reduction properties and magnetic corrosion of the negative electrode.

As another example, it may be added to the electrolyte used in the chemical conversion process to have the electrical properties of the electrode plate group, or it may be applied when replacing the electrolyte to meet the designed specific gravity after completion of the conversion.

In the general lead acid battery conversion process, the additive of the present invention is added to the sulfuric acid electrolyte (specific gravity 1.100 to 1.240), and it is mixed with water or sulfuric acid.

The sulfuric acid electrolyte prepared in this way is used as a primary electrolyte required for conversion of lead acid batteries and a secondary electrolyte for manufacturing finished products.

In the present invention, by adding the additive EMI-BF ₄ , the durability improvement effect is provided.

In order to provide the above functions, as shown in FIG. 1, the method of manufacturing an electrolyte solution of a lead acid battery for providing an improvement in liquid reduction characteristics and life of the present invention,

In the process of forming a lead acid battery, in the process of introducing the secondary electrolyte,

EMI-BF ₄ additive input step (S100) in which EMI-BF ₄ , an ionic liquid of 0.08 to 0.1 wt% compared to the 1.280 kg/L specific gravity of room temperature (10 to 25°C) electrolyte (H ₂ SO ₄ ), is added as an additive. );Wow

Then, the electrolyte solution completion step (S200) of completing the electrolyte solution by stirring at room temperature (10 to 25°C) for 1 to 24 hours.

Specifically, the EMI-BF ₄ additive input step (S100),

This is the step of introducing EMI-BF ₄ , an ionic liquid of 0.08 to 0.1 wt%, as an additive, compared to an electrolytic solution of 1.280 kg/L at room temperature (10 to 25°C) of dilute sulfuric acid (H ₂ SO ₄ ).

At this time, it was confirmed through experiments that the EMI-BF ₄ additive increased the amount of H2 gas generated when it was less than 0.08 wt% and exceeded 0.1 wt%, resulting in a decrease in the reduction durability test life, and decrease in capacity and CCA performance. Therefore, it would be desirable to properly add within the above range.

Thereafter, the electrolytic solution completion step (S200) is a step of completing the electrolytic solution by stirring at room temperature (10 to 25°C) for 1 to 24 hours, and since it is generally a lead acid battery electrolytic solution manufacturing process, a detailed description will be omitted.

Currently, as the use environment that requires lead acid batteries becomes increasingly severe, products with excellent charge/discharge characteristics of lead acid batteries are required, and new types of materials are being developed that meet the requirements.

The recent lead acid battery industry is striving to develop micro-hybrid or mild-hybrid automobile batteries in environments with high charging/discharging depth, and discharging that exceeds the requirements of general lead-acid batteries. There is no excessive drop of residual capacity at depth (Depth of discharge, hereinafter DOD) and high temperature durability (75 degrees SAE J2801) test is required by many customers.

Accordingly, in the present invention, EMI-BF ₄ , which is an ionic liquid, is introduced as an additive in order to improve liquid reduction properties, durability, and product life.

A lead acid battery manufactured without adding the additive of the present invention to the electrolyte used in the lead acid battery (BX80) manufactured by the applicant, and a lead acid battery manufactured after adding 0.08 to 0.1 wt% of EMI-BF ₄ , the additive of the present invention, to the electrolyte , followed by the addition of additives of EMI-BF ₄ 0.2 wt% of the present invention in the electrolytic solution in a lead-acid battery, adding additives in EMI-BF ₄ 0.05 wt% of the present invention in the electrolytic solution produced after the after manufacturing a lead-acid battery manufacturing reduction test And basic performance tests were conducted.

Table 1 is a test result table for reducing durability, and shows 21 days-3.95g/Ah, 42 days-5.28g/Ah when EMI-BF ₄ is not added, and MI-BF ₄ has a specific gravity of 1.280kg/L. When added in the range of 0.08 to 0.1 wt% of dilute sulfuric acid (H ₂ SO ₄ ) at room temperature (10 to 25°C) electrolyte, 21 days-1.95g/Ah, 42 days-2.95g/Ah.

Therefore, it was found that when the MI-BF ₄ of the present invention was added, the liquid reduction property was improved.

On the other hand, when the MI-BF ₄ additive is added in less than 0.08 wt% and in excess of 0.1 wt%, performance improvement can be expected than when not added, but rather, the generation of H2 gas increases, so that the reduction durability test life is reduced, and the capacity And it can be seen that the CCA performance is reduced, it will be preferable to add within the above range.

Table 2 is a basic performance test result table, and it was found that when EMI-BF ₄ was not added, the performance was lower than 70 Ah at 0N C20 at 60 Ah.

On the other hand, if MI-BF ₄ is added in the range of 0.08 ~ 0.1 wt% compared to the normal temperature (10 ~ 25℃) dilute sulfuric acid (H ₂ SO ₄ ) electrolyte with a specific gravity of 1.280 kg/L, the performance is better than 70 Ah. I could see that.

However, when the MI-BF ₄ additive is added in less than 0.08 wt% and in excess of 0.1 wt%, the basic performance is improved compared to when not added, but the performance is lower than the required 70 Ah, so the basic performance improvement is somewhat less than expected. It would be desirable to add within the above range as it provides results.

In addition, even in 1N C20, when the MI-BF ₄ additive was not added, it was found that the performance was 59 Ah, which was lower than 70 Ah, and MI-BF ₄ was used at room temperature (10 ~ 25℃) with a specific gravity of 1.280kg/L. Dilute sulfuric acid (H ₂ SO ₄ ) When added within the range of 0.08 ~ 0.1 wt% compared to the electrolyte, it was found that the performance was better than 70 Ah, 73 Ah.

However, when the MI-BF ₄ additive is added in less than 0.08 wt% and in excess of 0.1 wt%, the basic performance is improved compared to when not added, but the performance is lower than the required 70 Ah, so the basic performance improvement is somewhat less than expected. It would be desirable to add within the above range as it provides results.

As a result of this experiment, it was confirmed that when adding the EMI-BF ₄ additive, which is an ionic liquid of the present invention, it is possible to provide a lead acid battery with improved liquid reduction characteristics, durability and product life by reducing the generation of hydrogen gas.

In conclusion, through the present invention, by adding an ionic liquid, EMI-BF ₄ , to prepare an electrolytic solution and injecting it into a lead acid battery, magnetic corrosion of the negative electrode is prevented and hydrogen gas generation is reduced to reduce the liquid-reduction characteristics, durability, and product life. It is to provide an effect that can provide a lead acid battery with improved.

Although the present invention has been described with the accompanying drawings, this is only one of various embodiments including the gist of the present invention, and is intended to be easily implemented by those of ordinary skill in the art. As for the purpose, it is clear that the present invention is not limited to the above-described embodiments.

Accordingly, the scope of protection of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto by changes, substitutions, substitutions, etc. within the scope not departing from the gist of the present invention are the rights of the present invention. Will be included in the scope.

In addition, some configurations in the drawings are intended to more clearly describe the configuration, and it is clarified that they are exaggerated or reduced and provided. In addition, the reference numerals are for better understanding and do not mean that the shape and structure of the present invention are limited to the accompanying drawings.

S100: EMI-BF ₄ additive input step
S200: Electrolytic solution completion step

Claims (4)

In the electrolyte manufacturing method of a lead acid battery for providing liquid reduction characteristics and life improvement,
In the process of forming a lead acid battery, in the process of introducing the secondary electrolyte,
EMI-BF ₄ additive input step (S100) in which EMI-BF ₄ , an ionic liquid of 0.08 to 0.1 wt% compared to the 1.280 kg/L specific gravity of room temperature (10 to 25°C) electrolyte (H ₂ SO ₄ ), is added as an additive. );Wow
Then, the electrolyte solution completion step (S200) of completing the electrolyte by stirring at room temperature (10 ~ 25 ℃) for 1 ~ 24 hours; characterized by including,
In the EMI-BF ₄ additive input step (S100),
Addition of EMI-BF ₄ additive, which is an ionic liquid, prevents self-corrosion of the cathode, and reduces the generation of hydrogen gas to improve liquid reduction properties and durability.
When the required holding capacity of the lead acid battery is 70Ah, the capacity of the lead acid battery added with the EMI-BF ₄ additive is 73Ah. Way.
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