KR102424527B1 - Method for manufacturing electrode plate of lead acid battery with improved active material adhesion by applying conductive graphite silicon - Google Patents

Abstract

The present invention relates to a method for manufacturing an electrode plate of a lead-acid battery with improved active material adhesion by applying conductive graphite silicon, and more particularly, by applying conductive graphite silicon to the electrode plate as an active material and spraying it on the surface of the electrode plate to manufacture the electrode plate, It relates to a method for manufacturing an electrode plate of a lead-acid battery in which the adhesion of an active material is improved by applying conductive graphite silicon, which can improve the electrical conductivity of the electrode plate and the adhesion of the active material, thereby providing durability improvement of the lead-acid battery at high temperature.
Through the present invention, by improving the electrical conductivity of the lead-acid battery electrode plate and the adhesion of the active material, it is possible to provide an improvement in the durability of the lead-acid battery at high temperature.

Description

Method for manufacturing electrode plate of lead acid battery with improved active material adhesion by applying conductive graphite silicon

The present invention relates to a method for manufacturing an electrode plate of a lead-acid battery with improved active material adhesion by applying conductive graphite silicon, and more particularly, by applying conductive graphite silicon to the electrode plate as an active material and spraying it on the surface of the electrode plate to manufacture the electrode plate, It relates to a method for manufacturing an electrode plate of a lead-acid battery in which the adhesion of an active material is improved by applying conductive graphite silicon, which can improve the electrical conductivity of the electrode plate and the adhesion of the active material, thereby providing durability improvement of the lead-acid battery at high temperatures.

In general, lead-acid batteries used in automobiles and the like are secondary batteries that can be charged and discharged.

In this case, diluted sulfuric acid (H2SO4) is used as an electrolyte, lead dioxide (PbO2) is applied to the positive electrode (+) and sponge lead (Pb) is applied to the negative electrode (-) as an active material of the electrode plate. The active material of the positive electrode (+) and negative electrode (-) is changed (discharged) to lead sulfate (PbSO4), and when current flows from the outside, the lead sulfate is again converted into lead dioxide (+) and sponge lead (-) It uses the principle of changing (charging) into

Among them, the positive and negative electrodes consist of an active material that generates an electrical signal, a passage for the electrical signal, and a substrate that supports the active material. The performance and capacity of the lead acid battery change according to the weight of the active material, and the substrate is the lead acid battery It varies according to size.

The active material of a conventional lead-acid battery is generally based on lead powder and a sulfuric acid aqueous solution, and after mixing other additives according to the characteristics of the positive and negative electrodes, they are mixed to make the active material. The active material made in this way goes through a coating operation, which is a work applied to the substrate, and after aging and drying processes according to the positive/negative characteristics, the prepared positive and negative plates are alternately overlapped in several sheets. To this end, a non-conductive separator is installed, and the positive plate, the negative plate, and the separator are configured to form an electrode plate group.

A plurality of electrode plate groups are connected in series according to the capacity of the storage battery and are accommodated in the electric wire.

The accommodated electrode plate group undergoes a chemical conversion process that is supercharged so that it can have electrical properties. At this time, lead dioxide (PbO2) is formed in the active material of the positive electrode plate, and due to its characteristics, countless fine particles of oxidized lead are combined and the particles are rich in porosity. The electrolyte is designed to freely diffuse and penetrate the liver.

In addition, the active material of the negative plate is sponge-like lead (Pb), which is also rich in porosity and reactivity so that the electrolyte can freely diffuse and penetrate.

The products made in this way are finally available for use in the market.

During the above process, a separate aging and drying process is performed for each polarity in order to facilitate the supercharging process and improve the durability of the product.

The aging process of the positive electrode plate is an important process to increase the durability of the product. Lead (Pb), a component of the active material, is converted into lead oxide ( PbO) as well as change the crystal structure of the active material.

The negative plate can be aged and dried at the same time if left in the natural state without a separate process.

However, if sufficient aging and drying are not achieved, the electrode plate and the electrode plate stick together during the assembly process to form the electrode plate group, and the durability of the active material is reduced due to the presence of moisture, and the active material embedded between the substrates is easily dropped even by a small impact.

In the lead-acid battery made through this process, as the number of charging and discharging increases, the active material is more easily removed from the substrate due to the reaction of lead and sulfuric acid. This reduced the lifespan of lead-acid batteries to only 1 to 2 years normally.

In order to facilitate the initial charging of the product, if the negative electrode plate is not sufficiently aged and dried, product durability is deteriorated. In the case of the negative electrode plate, natural aging and drying are performed, but this is because the manufactured electrode plate contains moisture.

Prior documents related to the present invention include 'Patent Document 1', 'Patent Document 2', and 'Patent Document 3'.

Patent Document 1 relates to a method of synthesizing nano-sized silicon particles by ultrasonically treating porous silicon particles.

Silicon is a material that can replace carbon materials as an anode material for lithium secondary batteries.

In the case of the currently commercialized graphite material, the theoretical capacity is 372 mAh/g, but silicon has a theoretical capacity of 4000 mAh/g or more.

However, in the case of silicon, since the electrode deteriorates due to a large volume change (310%) in the process of alloying / de-alloying with lithium, there is a problem in that the capacity is rapidly reduced. has solved these problems.

Patent document 2 contains diatomaceous earth and carbon or contains diatomaceous earth as an active material raw material mainly composed of metal oxide for secondary batteries, and the content of carbon is minus 4.6 × 10 −1 multiplied by the content of diatomaceous earth is 4.9 Including the value indicated by the straight line drawn by the function represented by the linear equation for adding It relates to a negative electrode composition for a secondary battery, characterized in that it is completed from a mixture containing “S/A×100” mass percent or more with respect to the mass “A” of the active material raw material for the value “S” of the content of diatomaceous earth .

As a prior art, Patent Document 3, Registered Patent 10-0483246 'Anode active material, manufacturing method thereof, and lead-acid battery' discloses a technology related to an anode active material, characterized in that lignin is added to lead powder. have. However, the above technique can expect the effect of improving the life of the active material, but it is difficult to expect the effect of improving the conductivity and adhesion.

That is, there is a need to provide a new type of electrode plate manufacturing technology that can improve the durability of the lead-acid battery even at high temperatures by improving the electrical conductivity of the lead-acid battery electrode plate and improving the adhesion of the active material.

Korean Patent Publication No. 10-2004-0082876 (September 30, 2004) Japanese Laid-Open Patent Publication No. 2010-225564 (October 07, 2010) Republic of Korea Patent 10-0483246 (May 16, 2002)

Therefore, the present invention has been devised to solve the above problems of the prior art,

An object of the present invention is to improve the electrical conductivity of a lead-acid battery electrode plate and the adhesion of the active material by spraying the conductive graphite silicon on the electrode plate with an active material and then spraying it on the surface of the electrode plate, thereby improving the durability of the lead-acid battery at high temperature. to make it possible

In order to achieve the problem to be solved by the present invention, the electrode plate manufacturing method of the lead-acid battery in which the active material adhesion is improved by applying the conductive graphite silicon of the present invention,

A first step (S100) of preparing a negative electrode active material containing smoke, sulfuric acid, water, and a negative electrode additive using a mixing device; and

A second step (S200) of supplying conductive graphite silicon to the spraying device; and

A third step (S300) of applying the anode active material, which is the blended mixture, to a grid made of lead (S300); and

A fourth step (S400) of uniformly applying conductive graphite silicon by spraying the upper surface of the grid onto which the negative active material is applied using the spraying device (S400); and

By including; a fifth step (S500) of manufacturing a lead-acid battery electrode plate by putting the grid coated with the conductive graphite silicon into a drying device and curing it, thereby solving the problem of the present invention.

The electrode plate manufacturing method of a lead-acid battery with improved active material adhesion by applying conductive graphite silicon according to the present invention,

Conductive graphite silicon is applied to the electrode plate with an active material, and then sprayed on the surface of the electrode plate to prepare the electrode plate, thereby improving the electrical conductivity of the electrode plate of the lead acid battery and improving the adhesion of the active material, thereby improving the durability of the lead acid battery at high temperature.

In particular, it is possible to provide a life extension effect according to the improvement of durability.

1 is a process diagram of a method for manufacturing an electrode plate of a lead-acid battery in which adhesive strength of an active material is improved by applying conductive graphite silicon according to an embodiment of the present invention.

Hereinafter, since the present invention can apply various transformations and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail.

However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

The present embodiments are provided to explain the present invention in more detail to those of ordinary skill in the art to which the present invention pertains.

Therefore, the shape of each element shown in the drawings may be exaggerated to emphasize a clearer description, and in describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description omit

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

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

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

The singular expression includes the plural expression unless the context clearly dictates otherwise.

In the present invention, terms such as "comprises" or "have" are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

The electrode plate manufacturing method of a lead-acid battery having improved active material adhesion by applying conductive graphite silicon according to an embodiment of the present invention,

A first step (S100) of preparing a negative electrode active material containing smoke, sulfuric acid, water, and a negative electrode additive using a mixing device; and

A second step (S200) of supplying conductive graphite silicon to the spraying device; and

A third step (S300) of applying the anode active material, which is the blended mixture, to a grid made of lead (S300); and

A fourth step (S400) of uniformly applying conductive graphite silicon by spraying the upper surface of the grid onto which the negative active material is applied using the spraying device (S400); and

A fifth step (S500) of manufacturing a lead-acid battery electrode plate by putting the grid coated with the conductive graphite silicon into a drying device and curing it.

At this time, the first step (S100),

It is characterized in that the mixture is prepared by mixing 82 parts by weight of lead powder, 5 parts by weight of sulfuric acid having a specific gravity of 1.40, 11 parts by weight of water, and 1 part by weight of a negative electrode additive.

At this time, the conductive graphite silicon,

It is characterized in that it is 50 to 70 parts by weight compared to the smoke.

At this time, the fifth step (S500),

It is characterized in that the temperature of the drying device is set to a temperature of 300 to 400° C., and curing is performed for 1 hour to 7 hours.

At this time, by the electrode plate manufacturing method of the lead-acid battery in which the adhesive strength of the active material is improved by applying the conductive graphite silicon,

If the capacity of the manufactured lead-acid battery is 80Ah ~ 81Ah,

The lifespan is characterized in that it can provide a lifespan improvement of 28.5% in 306 cycles when conductive graphite silicon is applied in 238 cycles, which is a lifespan without conductive graphite silicon.

On the other hand, by the manufacturing method of the present invention, by providing a lead-acid battery including an electrode plate having improved active material adhesion by applying conductive graphite silicon, it is possible to provide an effect of increasing durability due to improved active material adhesion.

Hereinafter, it will be described in detail through an embodiment of the electrode plate manufacturing method of the lead-acid battery in which the adhesive strength of the active material is improved by applying the conductive graphite silicon according to the present invention.

1 is a process diagram of a method for manufacturing an electrode plate of a lead-acid battery in which adhesive strength of an active material is improved by applying conductive graphite silicon according to an embodiment of the present invention.

As shown in Figure 1, the electrode plate manufacturing method of the lead-acid battery in which the adhesive strength of the active material is improved by applying the conductive graphite silicon,

A first step (S100) of preparing a negative electrode active material containing smoke, sulfuric acid, water, and a negative electrode additive using a mixing device;

a second step (S200) of supplying conductive graphite silicon to the atomizer;

a third step (S300) of applying the anode active material, which is the blended mixture, to a grid made of lead;

a fourth step (S400) of spraying conductive graphite silicon on the upper surface of the grid on which the negative active material is applied using the spraying device to uniformly apply the same (S400);

A fifth step (S500) of manufacturing a lead-acid battery electrode plate by putting the grid coated with the conductive graphite silicon into a drying device and curing it.

The graphite described in the present invention is a conductive material, and it is good if it has conductivity without causing chemical change in the battery. For example, it may be graphite, carbon black, acetylene black, Ketjen black, and the like.

Specifically, the first step (S100) is a process of preparing a negative electrode active material containing smoke, sulfuric acid, water, and a negative electrode additive using a mixing device.

That is, the first step (S100) is,

82 parts by weight of lead powder, 5 parts by weight of sulfuric acid with a specific gravity of 1.40, 11 parts by weight of water, and 1 part by weight of a negative electrode additive to prepare a mixture.

Then, the mixture is stirred at a temperature of 50 to 75 degrees to obtain a mixture having a density of 60 to 80 g/In 3 .

After that, the second step (S200) is a process of supplying conductive graphite silicon to the spraying device.

That is, conductive graphite silicon is supplied to the spraying device, and preferably, 50 to 70 parts by weight of the smoke are prepared and supplied.

Conductive graphite silicon is added by 50 to 70 parts by weight based on the weight of the powder, and when the weight of the conductive graphite silicon is less than 50 parts by weight, the electrical conductivity of the electrode plate is similar to the conventional one, so it is difficult to expect performance improvement. , when it exceeds 70 parts by weight, it is difficult to expect more than 70 parts by weight of the life cycle, as demonstrated in the accelerated life test, and only provides a cause of price increase.

Therefore, it would be preferable to put the conductive graphite silicon within the above range.

Thereafter, the third step ( S300 ) is a process of applying the anode active material, which is the blended mixture, to the grid made of lead.

This is to apply the anode active material, which is a mixture mixed with a grid (electrode plate) made of lead, using a general coating method.

After that, the fourth step (S400) is a process of spraying conductive graphite silicon on the upper surface of the grid on which the negative active material is applied using a spraying device to uniformly apply it.

That is, the conductive graphite silicon contained in the spray device is uniformly applied.

For example, it is applied, that is, coated by using any one coating method selected from the group consisting of a doctor blade method, a spray coating method, and a spin coating method.

After that, the fifth step (S500) is a process of manufacturing a lead acid battery electrode plate by putting the grid coated with the conductive graphite silicon in a drying device and curing it.

Specifically, the temperature of the drying apparatus is set to a temperature of 300 to 400° C., and curing is performed for 1 hour to 7 hours.

When the temperature is less than the temperature range, the silicone coating layer is not cured properly, which may cause a problem in conductivity, and if it exceeds the temperature range, cracks may occur in the silicone coating layer. Therefore, curing within the above range is preferable.

On the other hand, in general, lead-acid batteries make an active material support by pressing nonwoven or paper tissue paper on the surface of the active material after applying the active material to the grid. This active material support (non-woven fabric or tissue paper) is characterized by acid resistance, heat resistance, and oxidation resistance.

However, since this active material support supports the active material only by pressing when applying the active material to the grid, it is easy to remove the active material from the grid depending on the user's usage conditions, operating conditions, and usage environment when it is installed in a vehicle and used. Accelerated drop-out, leading to reduced starting power or premature termination of lifespan.

In the present invention, by applying a conductive epoxy resin composite instead of such a press-type support, after applying the active material to the grid, spraying and drying processes are performed to improve the adhesion of the active material and to improve the early end of life of the lead acid battery. .

In addition, among the conductive epoxy resin composites, the conductive graphite silicone selected through numerous experiments in the present invention is based on a silicone-based polymer material, and the main polymer of the silicone rubber is polytimethylsiloxane, which is in the form of a chain rubber. Graphite powder is used as a filler, which is an adhesive with excellent heat resistance, acid resistance, weather resistance, and electrical properties. It is conductive particles that adhere to each other and connect the particles in a chain shape at the same time to show conductivity and adhesion.

Therefore, after the active material is applied to the grid, conductive graphite silicone is sprayed, uniformly applied to the surface of the active material, and then the paste on the surface of the active material is cured by drying at a high temperature (300 ~ 400 ℃) to produce a lead-acid battery electrode plate. will be.

As described above, in order to grasp the effect of the present invention, the active material is mixed and applied to the electrode plate, then conductive graphite silicon is sprayed on the electrode plate and coated, and then the paste is cured on the surface of the active material through drying at high temperature to cure the lead acid battery electrode plate After manufacturing and aging through the aging process, basic performance and lifespan tests were performed.

The conventional product to be described later refers to a product manufactured using a negative electrode plate coated with an active material used in the lead acid battery (BX80) manufactured by the applicant, and the improved product is an active material by applying conductive graphite silicon through the manufacturing method of the present invention. Refers to a product containing an electrode plate with improved adhesion.

In addition, conventional products and improved products with a final 70 Ah capacity (20 hour rate capacity) were produced through subsequent processes such as assembly and chemical conversion to give electrical conductivity to the substrate, and to prove the application effect of conductive graphite silicon For this purpose, chargeability and 50% DoD durability tests were conducted.

1) CA: Charge Acceptance test

After discharging a fully charged sample at room temperature (25±2℃) with a 5-hour rate current (17.5A based on 70Ah) for 2.5 hours, it is left at 0±2℃ for more than 12 hours.

After that, charge it with a constant voltage of 14.4V±0.1V and measure the current at 10 minutes of charging.

As a result of the test, it was found that the improved product increased the current by 15% in about 10 minutes compared to the conventional product due to high battery conductivity and charging efficiency.

division hour conventional products improvement




chargeability 1 minute 27.25 28.14 2 minutes 24.21 25.98 3 minutes 22.14 23.73 4 minutes 21.25 22.82 5 minutes 20.11 21.43 6 minutes 19.35 20.81 7 minutes 18.74 19.06 8 minutes 17.68 18.49 9 minutes 17.04 18.67 10 minutes 16.43 18.82

In the case of conventional products, an active material support is made by pressing nonwoven or paper tissue paper on the surface of the active material, and this active material support is used only to support the active material applied to the grid from falling off the grid, Tissue Paper) is characterized by acid resistance, heat resistance, and oxidation resistance.

However, since this active material support supports the active material only by pressing when applying the active material to the grid, it is easy to remove the active material from the grid depending on the user's usage conditions, operating conditions, and usage environment when it is installed in a vehicle and used. The drop-out of the engine is accelerated, leading to a decrease in starting power or premature termination of life.

However, the prior art has a problem in providing performance in the environment of the current society that requires increasingly high basic performance.

For example, since various electronic devices and communications are increasingly used in the vehicle, the use of electricity increases accordingly, and since it is frequently used at high temperatures due to global warming, it is necessary to guarantee the robustness of the battery performance.

Therefore, in the present invention, in order to improve this, conductive graphite silicon having excellent electrical conductivity and excellent adhesion is used.

This conductive graphite silicone is an adhesive with excellent heat resistance, acid resistance, weather resistance, and electrical properties. It is applied in the present invention by using conductive particles to adhere to each other and at the same time to connect particles in a chain shape to show conductivity and adhesion. will become

Therefore, it is possible to bring about high output and improved life expectancy, and finally, the basic performance and lifespan of the battery are improved.

Experimental data for this will be described later.

2) Accelerated life test (SAE J2801)

The lead-acid battery is subjected to 34 charge/discharge cycles in a 75°C water bath for about one week, similar to general vehicle conditions.

After performing 34 cycles, discharge at 200A for 10 seconds and when it maintains 7.2V or higher, proceed with the life test by repeating 34 cycles.

Also, if the charging current rises more than 15A or the discharge voltage falls below 12.0V during the cycle, the test is stopped.

Table 2 below shows the results of the SAE J2801 test, and shows the voltage when discharging at 200A for 10 seconds every 34 charge/discharge cycles.

cycle Graphite 0 parts by weight 30 parts by weight of graphite Graphite 50 parts by weight Graphite 70 parts by weight Graphite 90 parts by weight 34 11.82 11.83 11.85 11.87 11.89 68 11.76 11.77 11.80 11.83 11.87 102 11.72 11.73 11.78 11.80 11.84 136 11.69 11.71 11.76 11.79 11.82 170 11.65 11.68 11.74 11.77 11.80 204 11.55 11.61 11.69 11.70 11.76 238 11.43 11.45 11.60 11.63 11.70 272 7.2 or less 7.2 or less 11.49 11.55 11.65 306 7.2 or less 11.50 11.55 340 7.2 or less 7.2 or less

As shown in Table 2 above, as a result of the test, the lifespan is 238 cycles, but 50 parts by weight is sprayed if not coated with graphite silicon or 30 parts by weight is provided to the spray device and coated with a thickness of about 1 to 3 mm on the area of a general grid. The lifetime is 272 cycles when applied to the device and coated, and when 70 parts by weight is provided to the spray device for coating, the lifetime is 306 cycles and a lifespan improvement of 28.5% can be provided.

However, it can be seen that even if the conductive graphite silicon exceeding 70 parts by weight is provided to the spraying device and coated to a thickness of 1 to 3 mm, the lifespan does not further increase at 306 cycles. is 50 to 70 parts by weight, and among them, the most optimal value is 70 parts by weight, so it is preferable to add within the above range.

This is seen as a result of the decrease in the amount of sulfate accumulated in the active material as the charging efficiency is increased because the electrical conductivity between the active materials is improved, the electrical resistance is lowered, and the reaction surface area is increased.

That is, it can be seen that by showing a 28.5% improvement effect in lifespan compared to conventional products, by spraying conductive graphite silicon to form a coating layer, it can be seen that it has a positive effect on the lifespan increase.

Through the present invention, conductive graphite silicon is coated on the electrode plate with an active material and then sprayed on the surface of the electrode plate to produce the electrode plate, thereby improving the electrical conductivity of the electrode plate of the lead acid battery and improving the adhesion of the active material, thereby improving the durability of the lead acid battery at high temperature. do.

Those skilled in the art to which the present invention of the above content pertains will understand that the present invention may be implemented in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not restrictive.

S100: Step 1
S200: Step 2
S300: Step 3
S400: Step 4
S500: Step 5

Claims (6)

In the electrode plate manufacturing method of a lead-acid battery with improved active material adhesion by applying conductive graphite silicon,
A first step (S100) of preparing an anode active material containing smoke, sulfuric acid, water, and anode additives using a blending device (S100); and
A second step (S200) of supplying conductive graphite silicon to the spraying device; and
A third step (S300) of applying the anode active material, which is the blended mixture, to a grid made of lead (S300); and
A fourth step (S400) of spraying conductive graphite silicon onto the grid upper surface on which the negative active material is applied using the spraying device and uniformly applying the same (S400); and
A fifth step (S500) of manufacturing a lead-acid battery electrode plate by putting the grid coated with the conductive graphite silicon into a drying device and curing it;
The first step (S100) is,
It is characterized in that the mixture is prepared by mixing 82 parts by weight of smoked powder, 5 parts by weight of sulfuric acid having a specific gravity of 1.40, 11 parts by weight of water, and 1 part by weight of a negative electrode additive,
Characterized in obtaining a mixture of 60 to 80 g/In ³ density by stirring at a temperature of 50 to 75 degrees,
The conductive graphite silicon,
It is characterized in that it is 70 parts by weight relative to the smoke,
The fifth step (S500) is,
It is characterized in that the temperature of the drying device is set to a temperature of 300 ~ 400 ℃ and cured for 1 hour ~ 7 hours,
By the electrode plate manufacturing method of the lead acid battery,
If the capacity of the manufactured lead-acid battery is 80Ah ~ 81Ah,
The lifespan is characterized in that it can provide a lifespan improvement of 28.5% in 306 cycles when conductive graphite silicon is applied in 238 cycles, which is the lifespan without conductive graphite silicon,
In the case of chargeability, when conductive graphite silicon is not applied, it is 16.43A, and when conductive graphite silicon is applied, it is 15% increased to 18.82A. A lead-acid battery with improved active material adhesion by applying conductive graphite silicon pole plate manufacturing method.
delete delete delete delete By the manufacturing method of claim 1,
A lead-acid battery containing an electrode plate with improved active material adhesion by applying conductive graphite silicon.

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