KR102483433B1 - Electrolytic solution manufacturing method for providing electrode plate oxidation prevention - Google Patents

Abstract

The present invention relates to a method for preparing an electrolyte solution for preventing oxidation of electrode plates, and more particularly, to an electrolyte solution of a lead-acid battery prepared by adding malonic acid-bound fullerene as an additive to the lead-acid battery. It relates to a method for preparing an electrolyte solution for a lead-acid battery to provide reduction characteristics and lifespan improvement, characterized in that by reacting with active oxygen to prevent grid oxidation by removing active oxygen.
According to the present invention, when a malonic acid-bound fullerene is added and introduced into a lead-acid battery, the malonic acid functional group reacts with active oxygen and is combined, thereby removing active oxygen and preventing grid oxidation. .
In addition, by adding EMI-BF ₄ , which is an ionic liquid, to the above-described malonic acid-bound fullerene, an electrolyte solution is prepared and introduced into a lead-acid battery, thereby preventing self-corrosion of the cathode and reducing hydrogen gas generation, thereby improving the reduction characteristics and A lead-acid battery with improved durability and product life is provided.

Description

Electrolytic solution manufacturing method for providing electrode plate oxidation prevention

The present invention relates to a method for preparing an electrolyte solution for preventing oxidation of electrode plates, and more particularly, to an electrolyte solution of a lead-acid battery prepared by adding malonic acid-bound fullerene as an additive to the lead-acid battery. It relates to a method for preparing an electrolyte solution for a lead-acid battery for providing reduction characteristics and lifespan improvement, characterized in that by reacting and combining with active oxygen to prevent grid oxidation by removing active oxygen.

A lead-acid battery is a battery that can be charged and discharged by an oxidation-reduction reaction between two electrode plates made of lead and lead oxide, respectively, and sulfuric acid as an electrolyte.

It typically contains a plurality of positive and negative plates, alternating with negative and positive plates, with separators separating each plate from adjacent plates.

A space other than the electrode plate and the separator plate arranged in this way is filled with sulfuric acid as 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.

On the other hand, a lead-acid battery generally used in automobiles is a secondary battery capable of charging and discharging.

In this case, sulfuric acid (H2SO4) is used as an electrolyte, lead dioxide (PbO2) is applied to the positive electrode and spongy lead (Pb) is applied to the negative electrode as an active material of the electrode plate, and mixed to form a paste.

The active material thus prepared is applied to a substrate, which is a coating operation, and after undergoing an aging process and a drying process according to the characteristics of the positive and negative electrodes, an electrode plate group is manufactured by overlapping the prepared positive and negative plates.

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

The accommodated electrode group is subjected to a charging process to have electrical properties, so that it serves as a lead-acid battery.

In the case of the prior art Korean Patent Registration No. 10-1011859, a lead-acid battery and a method for manufacturing a lead-acid battery, 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 use environment requiring lead-acid batteries has become increasingly severe, products with superior charge and discharge characteristics than lead-acid batteries manufactured through the above-mentioned prior patent documents are required, and new products that meet the requirements are required. Form materials are being developed.

Recently, the lead-acid battery industry is striving to develop micro-hybrid or mild-hybrid automotive batteries in an environment with high charge/discharge depth, and durability that exceeds the requirements of general lead-acid batteries. this is being requested.

Therefore, a new technology capable of further improving durability is required.

Korean Patent Registration No. 10-1011859

Therefore, the present invention has been made to solve the above conventional problems,

An object of the present invention is to manufacture a lead-acid battery by adding fullerene to which malonic acid is bonded as an additive to an electrolyte solution of a lead-acid battery, and when the fullerene is added to the lead-acid battery, the malonic acid functional group reacts with active oxygen to form a grid oxidation by removing active oxygen. want to prevent

Another object of the present invention is to prepare an electrolyte by adding EMI-BF ₄ , an ionic liquid, as an additive to the electrolyte of a lead-acid battery and introduce it into a lead-acid battery, thereby preventing self-corrosion of the negative electrode and reducing the generation of hydrogen gas. It is intended to provide a lead-acid battery with improved charge reduction characteristics, durability, and product life.

In order to achieve the problem to be solved by the present invention, an electrolyte manufacturing method for providing electrode plate oxidation prevention according to an embodiment of the present invention,

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

A first additive inputting step (S100) of introducing malonic acid-decorated fullerene (MA-C60) as an additive in an amount of 2 to 3 wt% compared to sulfuric acid electrolyte; and

Thereafter, the electrolyte solution completion step (S200) of completing the electrolyte solution by stirring at room temperature (10 ~ 25 ℃) for 1 ~ 24 hours; by including, to solve the problem of the present invention.

Through the method of preparing an electrolyte for a lead-acid battery to provide reduction characteristics and lifespan improvement according to the present invention, when the fullerene to which malonic acid is added is added and introduced into the lead-acid battery, the malonic acid functional group reacts with active oxygen and is combined, By removing active oxygen, an effect of preventing grid oxidation is provided.

In addition, by adding ionic liquid EMI-BF ₄ to the fullerene to which the malonic acid is bonded, an electrolyte is prepared and introduced into a lead-acid battery to prevent self-corrosion of the negative electrode and reduce hydrogen gas generation, thereby improving the reduction characteristics and A lead-acid battery with improved durability and product life is provided.

1 is a process chart showing a method for manufacturing an electrolyte solution for preventing oxidation of an electrode plate according to an embodiment of the present invention.
2 is an example showing the state in which O ₂ ^- is bonded to malonic acid-decorated fullerene (MA-C60) introduced in the method for preparing an electrolyte solution for preventing oxidation of an electrode plate according to an embodiment of the present invention. It is also

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Since the present invention can have various changes and various forms, specific embodiments will be illustrated in the drawings and described in detail in the text.

However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms.

These terms are only used for the purpose of distinguishing one component from another.

For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention.

Terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention.

Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this application, the terms "comprise" or "have" are intended to designate that the features, steps, functions, components, or combinations thereof described in the specification exist, but other features, steps, functions, or components Or it should be understood that it does not exclude in advance the possibility of existence or addition of those in combination.

Meanwhile, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the present invention belongs.

Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

An electrolyte manufacturing method for providing electrode plate oxidation prevention according to an embodiment of the present invention,

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

A first additive inputting step (S100) of introducing malonic acid-decorated fullerene (MA-C60) as an additive in an amount of 2 to 3 wt% compared to sulfuric acid electrolyte; and

Thereafter, an electrolyte solution completion step (S200) of stirring for 1 to 24 hours at room temperature (10 ~ 25 ℃) to complete the electrolyte solution; characterized in that it includes.

At this time, after the first additive input step (S100), a second additive input step (S150) of introducing EMI-BF ₄ , which is an ionic liquid in an amount of 0.08 to 0.1 wt% compared to a sulfuric acid electrolyte having a specific gravity of 1.280 kg/L, as an additive. It is characterized in that it further includes;

At this time, the malonic acid functional group in the fullerene to which the malonic acid is bonded reacts with and is combined with the active oxygen, thereby removing the active oxygen and preventing grid oxidation.

At this time, in the second additive input step (S150),

It is characterized by adding an ionic liquid EMI-BF ₄ additive to prevent self-corrosion of the cathode and to reduce hydrogen gas generation to provide reduction characteristics.

At this time, by the electrolyte manufacturing method for providing the electrode plate oxidation prevention,

When the required storage capacity of the lead-acid battery is 70Ah, the storage capacity of the lead-acid battery to which the malonic acid-coupled fullerene additive and the EMI-BF ₄ additive are added is 75 to 78Ah.

In addition, by the electrolyte manufacturing method for providing the electrode plate oxidation prevention,

By providing a lead-acid battery to which an electrolyte solution containing a malonic acid-bound fullerene additive is applied, when the malonic acid-bound fullerene is added and introduced into the lead-acid battery, the malonic acid functional group reacts with active oxygen and is combined, resulting in active oxygen. Oxygen is removed to provide an effect of preventing oxidation of the grid.

Hereinafter, a method for preparing an electrolyte solution for preventing oxidation of an electrode plate according to the present invention will be described in detail through an embodiment.

In a conventional lead-acid battery, the electrode plate and sulfuric acid react with frequent charging and discharging, and thus have the following reaction formula.

As a result of the above reaction, water is decomposed and oxygen and hydrogen are generated.

At this time, as one electron (e ^- ) is transferred to the oxygen molecule (O ₂ ), a part of it is incompletely reduced to form a superoxide radical (•O ₂ ^- ).

The chemical formula is:

When these active oxygens stick to and oxidize Pb, it is called grid corrosion, and the chemical formula is as follows.

Due to grid corrosion, shorts due to grid growth may occur, and it is also a cause of active material dropout, which adversely affects performance and lifespan.

Therefore, in the present invention, the following manufacturing process is performed to solve the above problems.

That is, the method for preparing an electrolyte solution for preventing oxidation of an electrode plate according to the present invention,

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

A first additive inputting step (S100) of introducing malonic acid-decorated fullerene (MA-C60) as an additive in an amount of 2 to 3 wt% compared to sulfuric acid electrolyte; and

Then, an electrolyte solution completion step (S200) of completing the electrolyte solution by stirring at room temperature (10 ~ 25 ℃) for 1 ~ 24 hours; is included.

Specifically, in the secondary electrolyte input process in the process of forming a lead-acid battery, a first additive input step (S100) and an electrolyte completion step (S200) are passed through. The first additive input step (S100) is a sulfuric acid electrolyte solution. 2 to 3 wt% of malonic acid-decorated fullerene (MA-C60) is added as an additive.

Thereafter, the electrolyte solution is completed by stirring at room temperature (10 ~ 25 ℃) for 1 ~ 24 hours. (S200)

In general, grid corrosion may cause a short due to grid growth, and it is also the cause of active material dropout, which adversely affects performance and lifespan.

In the present invention, as a method for improving such a negative effect, active oxygen is removed by using fullerene to which malonic acid-decorated fullerene (MA-C ₆₀ ) is bonded as an electrolyte solution additive.

As shown in FIG. 2, the above MA-C ₆₀ is a material in which malonic acid is bonded to fullerene (C ₆₀ ) in which carbon atoms are connected in a pentagonal and hexagonal structure like a soccer ball, and the malonic acid functional group in MA-C ₆₀ is active. It reacts with oxygen and bonds with it.

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

Recently, the lead-acid battery industry is working hard to develop micro-hybrid or mild-hybrid automotive batteries in an environment with high charge/discharge depth, and discharge that exceeds the requirements of general lead-acid batteries. There is no excessive drop in residual capacity at depth (Depth of discharge, hereinafter DOD) and high-temperature durability (75 degrees SAE J2801) tests are being requested by many customers.

Accordingly, in order to improve the efficiency of a lead-acid battery, the present invention introduces not only fullerene to which malonic acid-decorated fullerene (MA-C ₆₀ ) is combined, but also EMI-BF ₄ , an ionic liquid, as an additive to the electrolyte solution. do.

As shown in FIG. 1, after the first additive input step (S100), 0.08 to 0.1 wt% of the ionic liquid EMI-BF ₄ is added as an additive to the sulfuric acid electrolyte solution with a specific gravity of 1.280 kg / L Second additive An input step (S150); will be added.

At this time, the malonic acid functional group in the fullerene to which the malonic acid is bonded is reacted with and combined with the active oxygen, thereby removing the active oxygen to prevent grid oxidation, but in another embodiment, in the second additive input step (S150) , EMI-BF ₄ additive, which is an ionic liquid, is added to prevent self-corrosion of the negative electrode and reduce hydrogen gas generation to provide reduction characteristics.

In the case of the prior art Korean Patent Registration No. 10-1011859, a lead-acid battery and a method for manufacturing a lead-acid battery, the molar concentration of aluminum (AL) ions was 0.01 to 0.3 mol/l, but ion analysis was 0.3 mol/l or more , will provide only the effect of Al (aluminum) ion.

However, the electrolyte manufacturing method according to the present invention is prepared by adding EMI-BF ₄ , an ionic liquid, as an additive to the electrolyte of a lead-acid battery, thereby preventing self-corrosion of the cathode and reducing the generation of hydrogen gas, thereby improving reduction characteristics and durability. And it is possible to provide a lead-acid battery with improved product life.

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

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

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

Recently, the lead-acid battery industry is making efforts to improve the durability of batteries for customers and the automobile industry who request the development of high-performance batteries in high-temperature regions. Since technical development is required, the present invention has been proposed in view of this.

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

Ionic liquids do not 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 lower, or, in particular, at room temperature (25 ° C), unlike the characteristics of existing salts, is called an ionic liquid.

By using the ionic liquid as an additive, it was confirmed through experiments that the hydrogen gas generated during the charging and discharging process of the lead-acid battery is reduced and the reduction property is increased.

During charging and discharging of the product, H ⁺ in the electrolyte is combined with electrons generated from the negative electrode (Pb) to become H ₂ Gas.

However, when EMI-BF ₄ is added, the cationic molecules of the material are adsorbed on the surface of the cathode by Van der Waals force and combine with the generated electrons to prevent hydrogen ions 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 ^-

2H+ + 2e ^- →H ₂ (turns into gas and flies away)

(2) Electron transfer process when adding EMI-BF ₄

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

Pb(IL ⁺ )ads + e ^- → Pb(IL)ads

Cationic molecules of EMI-BF4 described above are as follows.

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

When the EMI-BF ₄ is not added, H+ in the electrolyte is combined with electrons generated from 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 Van der Waals force, and combine with the generated electrons to reduce the generation of hydrogen gas.

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

Meanwhile, taking the above input process as an example, when manufacturing a lead acid battery, EMI-BF ₄ is added as an additive in an amount of 0.08 to 0.1 wt% based on the amount of the electrolyte.

Due to the high conductivity, special molecular structure and electron absorption of the ionic liquid, it helps to improve the lifespan of lead-acid batteries by preventing self-corrosion of the negative electrode and reducing charge.

As another example, it is okay to add it to the electrolyte used in the conversion process to have the electrical properties of the electrode group, and it is okay to apply it when replacing the electrolyte to meet the designed specific gravity after completion of conversion.

The additive of the present invention is added to a sulfuric acid electrolyte during a typical lead-acid battery conversion process, and has a form that is soluble in water or sulfuric acid and mixed with it.

The sulfuric acid electrolyte prepared in this way is used as a primary electrolyte required for forming a lead-acid battery and as a secondary electrolyte for manufacturing finished products.

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

In order to provide the above function, as shown in FIG. 1, the method for preparing an electrolyte solution for preventing oxidation of electrode plates of the present invention,

After the first additive input step (S100), a second additive input step (S150) of introducing 0.08 to 0.1 wt% of EMI-BF ₄ , an ionic liquid, as an additive compared to a sulfuric acid electrolyte solution having a specific gravity of 1.280 kg / L; will do

Specifically, the second additive input step (S150),

This is a step of adding EMI-BF ₄ , an ionic liquid, as an additive in an amount of 0.08 to 0.1 wt% compared to a room temperature sulfuric acid electrolyte having a specific gravity of 1.280 kg/L.

At this time, when the EMI-BF ₄ additive is less than 0.08 wt% and more than 0.1 wt%, the amount of H2 Gas generated increases, reducing the lifespan of the reduction durability test, and it was confirmed through experiments that the capacity and CCA performance decreased. Therefore, it would be desirable to properly add it within the above range.

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

Recently, the lead-acid battery industry is working hard to develop micro-hybrid or mild-hybrid automotive batteries in an environment with high charge/discharge depth, and discharge that exceeds the requirements of general lead-acid batteries. There is no excessive drop in residual capacity at depth (Depth of discharge, hereinafter DOD) and high-temperature durability (75 degrees SAE J2801) tests are being requested by many customers.

Accordingly, in the present invention, EMI-BF ₄ , an ionic liquid, is introduced as an additive in order to improve reduction characteristics, 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. , Lead-acid battery prepared after adding 0.2 wt% of EMI-BF ₄ as the additive of the present invention to the electrolyte, and lead-acid battery manufactured after adding 0.05 wt% of EMI-BF ₄ as the additive of the present invention to the electrolyte and basic performance tests were conducted.

Table 1 shows the results of the durability test for reduction in weight, and when EMI-BF ₄ is not added, 21 days - 3.95 g / Ah, 42 days - 5.28 g / Ah, and MI-BF ₄ has a specific gravity of 1.280 kg / L Room temperature (10 ~ 25 ℃) Dilute sulfuric acid (H ₂ SO ₄ ) When added within the range of 0.08 ~ 0.1 wt% compared to the electrolyte, 21 days - 1.95g / Ah, 42 days - 2.95g / Ah.

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

On the other hand, when the MI-BF ₄ additive is added in an amount of less than 0.08 wt% and more than 0.1 wt%, performance improvement can be expected compared to when the amount is not added, but rather, the amount of H2 gas generated increases, reducing the lifespan of the durability test and reducing the capacity And it can be seen that the CCA performance is reduced, so it would be preferable to add it within the above range.

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

On the other hand, when MI-BF ₄ is injected within the range of 0.08 ~ 0.1 wt% compared to the dilute sulfuric acid (H ₂ SO ₄ ) electrolyte at room temperature (10 ~ 25 ℃) with a specific gravity of 1.280 kg / L, the performance is better than 70 Ah and 71 Ah was found to be

However, when the MI-BF ₄ additive is added in an amount of less than 0.08 wt% and more than 0.1 wt%, the basic performance is improved compared to the case of no input, but the performance is lower than the required value of 70 Ah, so the basic performance improvement is somewhat less than expected. It would be desirable to add within the above range because it gives the result.

In addition, even in 1N C20, when MI-BF ₄ additive was not added, it was found that 59 Ah was lower than 70 Ah, and MI-BF ₄ was obtained by dilute sulfuric acid (H ₂ SO ₄ ) When injected within the range of 0.08 ~ 0.1 wt% compared to the electrolyte, it was found that 73 Ah performed better than 70 Ah.

However, when the MI-BF ₄ additive is added in an amount of less than 0.08 wt% and more than 0.1 wt%, the basic performance is improved compared to the case of no input, but the performance is lower than the required value of 70 Ah, so the basic performance improvement is somewhat less than expected. It would be desirable to add within the above range because it gives the result.

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

Table 3 is a table of basic performance test results, and it can be seen that 60 Ah is lower than 70 Ah at 0N C20 when malonic acid-decorated fullerene (MA-C60) is not added.

On the other hand, when malonic acid-decorated fullerene (MA-C60) was added in the range of 2 to 3 wt% compared to the sulfuric acid electrolyte, it was found that 70 Ah performed better than 70 Ah.

However, when the MA-C60 additive is added in an amount of less than 2 wt% and more than 3 wt%, the basic performance is improved compared to when the additive is not added, but the performance is lower than the required value of 70 Ah, so the basic performance improvement is somewhat less than expected. Since it provides, it would be preferable to add it within the above range.

In addition, even in 1N C20, when the MA-C60 additive was not added, it was found that the performance was 59 Ah, which was lower than 70 Ah, and when the MA-C60 additive was added in the range of 2 ~ 3 wt% compared to the sulfuric acid electrolyte, the performance was higher than 70 Ah. It was found that 71 Ah was excellent.

However, when the MMA-C60 additive is added in an amount of less than 2 wt% and more than 3 wt%, the basic performance is improved compared to when the additive is not added, but the performance is lower than the required value of 70 Ah, so the basic performance improvement is somewhat less than expected. Since it provides, it would be preferable to add it within the above range.

Table 4 above is a basic performance test result table, when malonic acid-decorated fullerene (MA-C60) and EMI-BF ₄ additives are not added, performance is lower than 70 Ah in 0N C20 60 Ah Could know.

On the other hand, malonic acid-decorated fullerene (MA-C60) is added within the range of 2 to 3 wt% compared to the sulfuric acid electrolyte, and the EMI-BF ₄ additive is added within the range of 0.08 to 0.1 wt% compared to the sulfuric acid electrolyte. When injected, it was found that 75 Ah performed better than 70 Ah.

However, when less than 2 wt% of the MA-C60 additive and less than 0.08 wt% of the EMI-BF ₄ additive, or more than 3 wt% of the MA-C60 additive and more than 0.1 wt% of the EMI-BF ₄ additive are added. Although the basic performance is improved compared to the case of non-input, it is preferable to add it within the above range because the performance is lower than the required value of 70 Ah, so the basic performance improvement provides somewhat less than expected results.

In addition, even in 1N C20, when the MA-C60 additive and the EMI-BF ₄ additive were not added, it was found that the performance was 59 Ah, which was lower than 70 Ah. When the EMI-BF ₄ additive was added within the range of 0.08 to 0.1 wt% compared to the sulfuric acid electrolyte, it was found that 78 Ah performed better than 70 Ah.

However, when less than 2 wt% of the MA-C60 additive and less than 0.08 wt% of the EMI-BF ₄ additive, or more than 3 wt% of the MA-C60 additive and more than 0.1 wt% of the EMI-BF ₄ additive are added. Although the basic performance is improved compared to the case of non-input, it is preferable to add it within the above range because the performance is lower than the required value of 70 Ah, so the basic performance improvement provides somewhat less than expected results.

Therefore, when the above-mentioned MA-C60 additive and EMI-BF ₄ additive are injected into the electrolyte in an amount within the set range to improve the basic performance, the effect of preventing grid oxidation by removing active oxygen and the self-corrosion of the cathode It is to provide a lead-acid battery with improved reduction characteristics, durability, and product life by preventing hydrogen gas generation and reducing hydrogen gas generation.

In conclusion, through the present invention, when prepared by adding malonic acid-bound fullerene and put into a lead-acid battery, the malonic acid functional group reacts with and combines with active oxygen, thereby removing active oxygen and preventing grid oxidation. will do

In addition, by adding ionic liquid EMI-BF ₄ to the fullerene to which the malonic acid is bonded, an electrolyte is prepared and introduced into a lead-acid battery to prevent self-corrosion of the negative electrode and reduce hydrogen gas generation, thereby improving the reduction characteristics and A lead-acid battery with improved durability and product life is provided.

Although the present invention has been described with the accompanying drawings, this is only one example of various embodiments including the gist of the present invention, and is intended to be easily practiced by those skilled in the art. As an object, it is clear that the present invention is not limited to the embodiments described above.

Therefore, the protection scope of the present invention should be construed by the following claims, and all technical ideas within the equivalent range by change, substitution, substitution, etc. within the scope of the present invention are the rights of the present invention. will be included in the scope.

In addition, it is clear that some configurations in the drawings are provided exaggerated or reduced than actual ones for more clearly explaining the configuration. In addition, claim numerals are provided only to aid understanding and do not mean that the shape and structure of the present invention are limited to the accompanying drawings.

S100: First additive input step
S150: Second additive input step
S200: Electrolyte completion step

Claims (6)

In the electrolyte manufacturing method for providing electrode plate oxidation prevention,
In the secondary electrolyte input process in the process of forming a lead-acid battery,
A first additive inputting step (S100) of introducing malonic acid-decorated fullerene (MA-C60) as an additive in an amount of 2 to 3 wt% compared to sulfuric acid electrolyte; and
Thereafter, an electrolyte solution completion step (S200) of completing the electrolyte by stirring at room temperature (10 ~ 25 ℃) for 1 ~ 24 hours; Electrolytic solution manufacturing method for providing electrode plate oxidation prevention, characterized in that it includes.
According to claim 1,
After the first additive input step (S100), a second additive input step (S150) of introducing 0.08 to 0.1 wt% of ionic liquid EMI-BF ₄ as an additive compared to a sulfuric acid electrolyte having a specific gravity of 1.280 kg/L (S150); An electrolyte manufacturing method for providing electrode plate oxidation prevention, characterized in that it comprises.
According to claim 1,
Electrolyte manufacturing method for preventing electrode plate oxidation, characterized in that the malonic acid functional group in the fullerene to which the malonic acid is bonded reacts with active oxygen and thereby prevents grid oxidation by removing active oxygen.
delete delete The method according to claim 1, by the method for preparing an electrolyte solution for preventing oxidation of the electrode plate,
A lead-acid battery with an electrolyte containing a fullerene additive combined with malonic acid.

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