KR20200046405A - Method for manufacturing electrolyte containing phase change material - Google Patents

Abstract

The present invention relates to a method for manufacturing an electrolyte containing a phase change material (PCM) and, more specifically, to a method for manufacturing an electrolyte containing a PCM, in which the PCM is added as an additive added to the electrolyte inputted to a chemical conversion process of a lead-acid battery so thermal energy due to weather and thermal energy generated from a vehicle engine are absorbed to lower the internal temperature of the lead-acid battery. According to the present invention, since the PCM is added, the thermal energy due to weather and the thermal energy generated from a vehicle engine are absorbed so the internal temperature of the lead-acid battery is lowered, thereby increasing average lifespan of the lead-acid battery. According to the present invention, the PCM is paraffin wax.

Description

Method for manufacturing electrolyte containing phase change material

The present invention relates to a method for manufacturing an electrolyte solution containing a phase change material, and more specifically, as an additive added to an electrolyte solution introduced in a chemical conversion process of a lead acid battery, by adding a phase change material (PCM), thermal energy due to climate The present invention relates to a method of manufacturing an electrolyte solution containing a phase change material capable of absorbing thermal energy generated from an automobile engine and lowering the temperature inside the lead acid battery.

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

It generally includes a plurality of positive and negative plates, and the negative and positive plates are alternately arranged with a separator that isolates each plate from adjacent plates.

The spaces other than the polar plates and separators thus arranged are filled with electrolyte, sulfuric acid.

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

However, when using lead-acid batteries for atrial use only, periodic retention is required, and there is a problem of corrosion and sulfation of the electrode plate due to the stratification of sulfuric acid, which is an electrolyte, during large-sized, and this leads to a shortage of battery life. Shortened, resulting in a significant cost burden.

In addition, there is a risk of explosion due to gas generated during overcharging.

As an alternative to the corrosion and oxidation problems of the electrode plate, sulfuric acid, an electrolyte, is included in an inorganic gel or an absorptive glass mat (AGM), but in the case of an absorbing glass mat, a problem of heat generation occurs during use. The stratification of sulfuric acid is greater than that of gels.

In particular, in the case of a large industrial battery, since the layering phenomenon of sulfuric acid is small and the content of sulfuric acid is relatively high, a gel electrolyte having excellent performance is mainly used.

Inorganic gels are generally prepared by gelling inorganic particles such as fumed silica or colloidal silicate in an aqueous sulfuric acid solution.

In this case, since the amount of gas generated decreases due to oxygen recombination and the storage battery can be used in a sealed state, maintenance such as periodic addition of the electrolyte is unnecessary and the risk of explosion is small.

In addition, since the layering of the electrolytic solution is small, corrosion and sulfation of the electrode plate are reduced, resulting in a longer service life.

However, these inorganic gel electrolytes have problems such as low charge capacity, life performance, and cracking of the gel due to repeated charge and discharge compared to sulfuric acid.

In general, it is known that when the proportion of inorganic particles in the inorganic gel increases, physical strength such as physical deformation such as cracking of the gel during use decreases, whereas the filling capacity decreases.

In order to solve these problems of the inorganic gel electrolyte, a small amount of a binder is used, and the binder strengthens the bonding between the inorganic particles, thereby increasing mechanical strength without lowering the filling capacity.

On the other hand, lead-acid batteries generally used in automobiles and the like are secondary batteries capable of charging and discharging.

Sulfuric acid (H 2 SO 4) is used as the electrolyte, and lead dioxide (PbO2) is applied to the positive electrode as the active material of the electrode plate, sponge-like lead (Pb) is applied to the negative electrode, and mixed to make a paste.

The active material thus produced is applied to the substrate, which is a coating operation, and after the aging process and drying process according to the characteristics of the anode and the cathode, the prepared anode plate and the cathode plate are overlapped to manufacture the electrode plate group.

A number of the electrode plate groups are connected in series according to the storage battery capacity, and are accommodated in a casing.

The accommodated electrode plate group is charged with a chemical conversion process so as to have electrical properties to serve as a lead acid battery.

The present invention is a method of adding a phase change material (PCM) as an additive in the production of a sulfuric acid electrolyte solution used in a filling process.

In the case of a lead-acid battery and a method of manufacturing a 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 the lead acid battery.

However, as the current use environment for lead-acid batteries becomes increasingly severe, the charge-discharge characteristics of lead-acid batteries require products that are superior to lead-acid batteries manufactured through the above-mentioned prior patent documents, and are new to meet the requirements. Form materials are being developed.

In recent years, the lead acid battery industry is focusing on the development of micro-hybrid or mild-hybrid automotive batteries in environments with high charging / discharging depths, and surpassing the requirements of general lead-acid batteries. This is required.

Therefore, a new technology capable of increasing the life of the lead acid battery by lowering the internal temperature to further improve durability is required.

Republic of Korea Patent Registration No. 10-1011859

Therefore, the present invention has been devised to solve the conventional problems,

As an additive added to the electrolyte to be put into the chemical conversion process of a lead acid battery, by adding a phase change material (PCM), it is possible to lower the temperature inside the lead acid battery by absorbing heat energy caused by the climate and heat energy generated from an automobile engine. .

In order to achieve the problem to be solved by the present invention, the method of manufacturing an electrolyte solution comprising a phase change material according to an embodiment of the present invention,

As an additive added to the electrolyte to be put into the chemical conversion process of a lead acid battery, by adding a phase change material (PCM), it is possible to absorb heat energy caused by the climate and heat energy generated from an automobile engine and lower the temperature inside the lead acid battery. Is done.

At this time, preferably, the phase change material (PCM),

It is characterized by being a paraffin wax.

In addition, the phase change material (PCM),

It is characterized by adding 0.03 to 0.1 parts by weight relative to 1 part by weight of the electrolyte.

By adding the phase change material (PCM) as an additive added to the electrolyte input to the chemical conversion process of the lead acid battery through the method of manufacturing the electrolyte solution containing the phase change material according to the present inventors, heat energy caused by the climate and heat energy generated from the automobile engine By absorbing to be able to lower the temperature inside the lead acid battery, it provides an effect of increasing the average life of the lead acid battery.

1 is an exemplary view showing the principle of a general phase change material.
Figure 2 is a durability test comparison graph between the actual product and the conventional product according to the method for producing an electrolyte containing a phase change material according to an embodiment of the present invention.

Method for producing an electrolyte solution comprising a phase change material according to an embodiment of the present invention,

As an additive added to the electrolyte to be put into the chemical conversion process of a lead acid battery, by adding a phase change material (PCM), it is possible to absorb heat energy caused by the climate and heat energy generated from an automobile engine and lower the temperature inside the lead acid battery. Is done.

At this time, the phase change material (PCM),

It is characterized by being a paraffin wax.

At this time, the phase change material (PCM),

It is characterized in that it is 0.03 to 0.1 parts by weight compared to 1 part by weight of the electrolyte.

Hereinafter, it will be described in detail through an embodiment of the method of manufacturing an electrolyte solution comprising a phase change material according to the present invention.

In the case of a lead-acid battery and a method of manufacturing a 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.

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

However, in the case of the present invention, by adding a phase change material (PCM) as an additive added to the electrolyte to be introduced into the chemical conversion process of the lead acid battery, the heat energy generated by the climate and the heat energy generated from the automobile engine are absorbed and the inside of the lead acid battery. By allowing the temperature to be lowered, an effect of increasing the average life of the lead acid battery is provided.

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 to meet requirements such as grid growth and corrosion inhibition, and improvement of charge and discharge characteristics of products.

In recent years, the lead acid battery industry is making efforts to improve the durability of batteries for customers and the automotive industry, who are requesting the development of high-temperature areas and high-performance batteries. It can be kept stable, or can be increased more than before.

Therefore, the present invention, by adding the above-described phase change material (PCM) to the electrolyte solution, by absorbing the thermal energy generated by the vehicle engine and thermal energy caused by the climate to lower the temperature inside the lead acid battery, the average life of the lead acid battery Will increase.

In a conventional lead acid battery, the electrode plate and sulfuric acid react as they undergo frequent charging and discharging, and have the following reaction formula.

^{_{Anode: PbO 2 + SO4 2- + 4H}} - + 2e - <-> PbSO 4 + 2H 2 0

Cathode: Pb + + SO4 ^2- <-> PbSO ₄ + 2e-

At this time, the phase change material (PCM) of the present invention,

It is characterized by being a paraffin wax.

As shown in FIG. 1, the phase change material PCM (Phase change material) is a material capable of absorbing or releasing surrounding heat while the state of the material changes, and specifically, the effect of absorbing or releasing latent heat possessed by the material. Refers to a material used for the purpose of storing energy or maintaining a constant temperature.

Here, latent heat refers to heat absorbed or released at the same temperature when a substance changes phase, that is, from solid to liquid or liquid to solid, liquid to gas or gas to liquid, and latent heat is sensible heat, that is, It is much greater than the amount of heat absorbed or released in the absence of phase change.

Therefore, the phase change material (PCM) is to increase the temperature gradually when the ambient temperature is high, and gradually decrease the temperature when the ambient temperature is low, so that it can maintain a cool state for a long time in the summer when the ambient temperature is high, In winter, when the ambient temperature is low, it has a function to maintain a warm state for a long time.

In particular, since the lead-acid battery shows a difference in performance depending on the ambient temperature, performance degradation occurs due to the ambient temperature in winter, and accordingly, the replacement cycle is shortened.

Therefore, paraffin wax is added as described above to increase the life.

Examples of the phase change material include Paraffin C18 (45-55%), the phase change temperature of which is 28 ° C, and the heat value is 244 (KJ / kg).

The present inventor put the above-mentioned model of the phase change material into the electrolyte, and the results are shown in FIG. 2.

The above paraffin wax is a mixture of hydrocarbons.

In addition, normal paraffin is very stable.

The paraffin-based phase change material selected in the present invention has a low density, a small volume expansion, and is an organic material, and therefore does not dissolve in an electrolyte (hydrophilic).

In addition, since the corrosion resistance is small, it can be used in the electrolyte, so it is used as an additive to the electrolyte.

Therefore, by adding paraffin to the electrolyte, it absorbs thermal energy from the climate and thermal energy from the automobile engine, thereby reducing the temperature of the entire battery.

On the other hand, the phase change material (PCM),

It is characterized in that it is 0.03 to 0.1 parts by weight compared to 1 part by weight of the electrolyte.

For example, about 6 to 7 liters of electrolytic solution enters the lead acid battery. Since the lead acid battery is usually divided into 6 zones, about 1 liter per zone is input.

At this time, about 30 to 100 g of paraffin wax is added compared to 1 liter of the electrolyte.

If added below 30 g, the heat of absorption is low, it is difficult to exert re-function, and when it exceeds 100 g, the weight of the lead acid battery increases, fuel efficiency may deteriorate, and paraffin wax itself is a high-grade material, so unnecessary manufacturing cost increases. It is preferable to add paraffin wax within the above range.

In addition, as typical phase change materials, tetradecane, eic acid, octadecane, hexadecane, propionamide, naphthalene, acetamide, stearic acid, polyglycol, paraffin wax, palmitic acid, myristic acid, lignocerate, campen, One or more selected from the group consisting of 3-heptananecanone, polyethylene glycol, tetradecane, cyanamide, lauric acid, carpolone, trimyristrin, hexadecanone, capric acid, caprylic acid and polyglycol It can be used, but preferably, paraffin wax is selected.

On the other hand, the specification of the durability test of Figure 2 is a test method for measuring the cycle until the end of the life of the lead-acid battery repeatedly charging / discharging.

One cycle is charged for 40 minutes at 14.4 V, and discharged for 30 minutes at 7 x I20 (current value for 20 hours).

The cycle is repeated, and if the lead acid battery is 10 V or less, the battery is judged to end its life and the test is stopped.

This test is commonly referred to as Continous 17.5% Depth of Dischrage, and has a slightly different format for international standards and each automobile company.

The general international standard is to perform full charging every 85 cycles so as not to be continous, but the test standard in FIG. 2 is a separate standard of an automobile company for more severe charging and discharging.

As shown in Fig. 2, the conventional product shows 695 cycles, but the lead acid battery of the present invention shows 1,530 cycles, so the durability improvement effect obtained by adding additives is improved by about 2 times or more than the conventional product. It is obvious that the effect of increasing the lifespan of the lead acid battery can naturally increase.

As an embodiment, it may be added to the electrolyte used during the chemical conversion process to enable the electrical properties of the electrode plate group, or may be applied when replacing the electrolyte to replace the designed specific gravity after completion of chemical conversion.

The electrolyte containing the phase change material thus prepared is used as a primary electrolyte required for the formation of a lead acid battery and a secondary electrolyte for manufacturing a finished product.

In conclusion, through the present invention, by adding a phase change material (PCM) as an additive added to the electrolyte to be introduced into the chemical conversion process of a lead acid battery, it absorbs heat energy generated by the climate and heat energy generated from an automobile engine, and is inside the lead acid battery. By allowing the temperature to be lowered, an effect of increasing the average life of the lead acid battery is provided.

Although the present invention has been described with reference to the accompanying drawings, this is only one embodiment of various embodiments including the gist of the present invention, and it is intended to be easily carried out by a person skilled in the art. It is clear that there is a purpose, and the present invention is not limited to the above-described embodiment.

Therefore, the protection scope of the present invention should be interpreted by the following claims, and all technical spirits within the equivalent range by change, substitution, replacement, etc. without departing from the gist of the present invention are the rights of the present invention. Will be included in the scope.

In addition, some of the components of the drawings are intended to explain the configuration more clearly, and it is clearly provided that it is exaggerated or reduced than the actual one. In addition, the claims are not intended to limit the shape and structure of the present invention to the accompanying drawings only to aid understanding.

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Claims (3)

In the electrolytic solution manufacturing method comprising a phase change material,
As an additive added to the electrolyte to be put into the chemical conversion process of a lead acid battery, by adding a phase change material (PCM), it is possible to absorb heat energy caused by the climate and heat energy generated from an automobile engine and lower the temperature inside the lead acid battery. Method for producing an electrolyte containing a phase change material.
According to claim 1,
The phase change material (PCM),
Method for producing an electrolyte solution comprising a phase change material, characterized in that the paraffin wax.
According to claim 1,
The phase change material (PCM),
Method for producing an electrolyte containing a phase change material, characterized in that 0.03 to 0.1 parts by weight compared to 1 part by weight of the electrolyte.

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