WO2019059501A1 - Lead-acid battery electrode and lead-acid-based storage battery system comprising same - Google Patents

Abstract

The present invention relates to a lead-acid-based storage battery system, and relates to a lead-acid battery electrode in which electrode lifetime and performance are enhanced by forming a porous coating layer on the electrode surface, and a lead-acid-based storage battery system comprising same.

Description

Electrode for lead acid battery and lead acid battery system containing the same

The present invention relates to a lead-acid battery cell system, and more particularly, to a lead-acid battery electrode having improved electrode lifetime and performance by forming a porous coating layer on the electrode surface, and a lead-acid battery cell system including the same.

BACKGROUND OF THE INVENTION Portable rechargeable energy storage devices, such as rechargeable electrochemical batteries and capacitors, are becoming increasingly essential as a driving force in the modern transportation and communications sector.

Lead accumulators have evolved over time, as the demand for sources of mobile power grows. In certain service sectors, a flooded lead-acid battery can be operated with a partial state of charge (PSoC), for example, approximately 50 to 80% charged state, It differs from the usual SLI (start, ignition, and ignition) that is activated. For example, a battery of a hybrid electric vehicle (HEV) can operate at PSoC, for example, at about 50 to 80% charge. Thereby, the battery can undergo low charge / recharge cycles, and the dissociation of the water does not suffer from overcharging which produces hydrogen and oxygen and is mixed with stratified acid in the cell have.

The improved lead-acid based battery system is a technology developed to improve the life of existing lead-acid batteries. When the carbon mixture layer is applied to the surface, it prevents localized lead sulphate (PbSO ₄ ) crystal growth due to the increased surface electrical conductivity, ₂ / Pb to improve battery life.

More specifically, in the charging / discharging process, the lead crystal (Pb), which is an electrode active material, changes to lead ion (Pb ²⁺ ). Pb ²⁺ ions form lead sulphate (PbSO ₄ ) crystals during the discharge process. As lead sulphate crystals grow, the contact area between the electrode surface and the electrolyte decreases and the surface electroconductivity decreases, forming a local electron transfer channel Partly, lead sulfate crystals are formed to a large extent, the utilization ratio of the electrode active material is decreased, and PbO ₂ / Pb can not be returned to the electrolyte during the charging process. However, when the carbon mixture layer is applied to the electrode surface, it is possible to prevent the local growth of lead sulfate crystals due to the increased surface electroconductivity and to recover PbO ₂ / Pb and improve the life of the battery.

However, the carbon layer is applied to the cathode electrode to prevent the electrolyte from flowing smoothly on the surface of the cathode. As a result, the cathode surface resistance Resulting in a problem that the capacity is rather lowered or the lifetime is shortened.

Accordingly, it is an object of the present invention to provide an electrode for a lead-acid battery having a structure which can prevent the flow of an electrolyte generated due to a carbon layer coated on a lead-acid battery negative electrode,

Another object of the present invention is to provide a lead acid storage battery system in which the capacity of a cathode electrode can be improved and the system life can be improved by employing an electrode having a structure in which an electrolyte can smoothly contact an electrode.

The objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

In order to achieve the above-described object of the present invention, the present invention provides an electrode support comprising: an electrode; And a water soluble polymer-containing carbon layer formed on the surface of the support.

In a preferred embodiment, the water soluble polymer-containing carbon layer includes a high specific surface area carbon material, a high conductivity carbon material, a water soluble polymer and a binder.

In a preferred embodiment, the water soluble polymer is included in an amount of 1 to 30 parts by weight per 100 parts by weight of the sum of the high specific surface area carbon material, the high conductivity carbon material and the binder.

In a preferred embodiment, the high specific surface area carbon material, the high conductivity carbon material, and the binder are 25 to 80 wt%, 15 to 70 wt%, and 1 to 40 wt%, respectively, of the total content.

In a preferred embodiment, the size of the water-soluble polymer is 0.1 μm to 100 μm.

In a preferred embodiment, the high specific surface area carbon material has a specific surface area of 500 to 3,000 m ² / g.

In a preferred embodiment, the highly conductive carbon material has an electric conductivity of 20 S / m or more.

In a preferred embodiment, the binder is at least one selected from the group consisting of polyester, PET, PTFE, PVdF, and CMC.

In a preferred embodiment, the water soluble polymer is selected from the group consisting of polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl pyrrolidone (PVP) Or more.

In a preferred embodiment, the water soluble polymer-containing carbon layer is formed to a thickness of 10 탆 to 500 탆.

In a preferred embodiment, when the water soluble polymer-containing carbon layer is brought into contact with the electrolytic solution, the water soluble polymer is dissolved to form pores.

The present invention also provides a lead-acid based battery system comprising any one of the electrodes described above.

In a preferred embodiment, the electrode is a cathode.

First, the electrode for a lead-acid battery of the present invention forms pores in the carbon layer so that the electrolyte moves more smoothly through the carbon layer, thereby reducing the resistance and improving the capacity of the battery. In addition, Can grow inside the pores without blocking the surface of the electrode, thereby improving the life of the electrode.

Further, the lead-acid battery system of the present invention can improve the capacity of the cathode electrode and improve the life of the system by adopting the electrode having a structure in which the electrolyte can smoothly contact with the electrode, thereby realizing a secondary battery having excellent cycle performance have.

The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.

FIG. 1 is a graph showing a capacity evaluation test result using an electrode for a lead-acid battery obtained according to an embodiment of the present invention.

FIG. 2 is a graph of a life evaluation test result using an electrode for a lead-acid battery obtained according to an embodiment of the present invention.

Although the terms used in the present invention have been selected as general terms that are widely used at present, there are some terms selected arbitrarily by the applicant in a specific case. In this case, the meaning described or used in the detailed description part of the invention The meaning must be grasped.

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

However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals used to describe the present invention throughout the specification denote like elements.

The technical feature of the present invention resides in an electrode for a lead-acid battery having a structure in which a plurality of pores can be formed in a carbon layer when an electrolyte and a carbon layer are brought into contact with each other by including a water-soluble polymer in a carbon layer formed on an electrode surface of a lead-

That is, by introducing a water-soluble polymer into the carbon layer coated on the surface of the lead-material electrode support, when the electrode is assembled and the electrolyte is permeated, the water-soluble polymer contained in the carbon layer is dissolved in the electrolytic solution, And the electrolyte moves more smoothly through the pores to smooth the contact between the electrode and the electrolyte. As a result, the resistance is reduced to improve the capacity of the battery, and the lead sulfate crystals produced in the charging / It is possible to contribute to the improvement of the lifetime of the battery.

Accordingly, the present invention provides an electrode support comprising: an electrode; And a water soluble polymer-containing carbon layer formed on the surface of the support.

The water soluble polymer-containing carbon layer may comprise a high specific surface area carbon material, a high conductivity carbon material, a water soluble polymer and a binder.

Particularly, the water-soluble polymer is a certain amount of the carbon material, and can be contained in an amount of 1 to 30 parts by weight per 100 parts by weight of the total amount of the high specific surface area carbon material, the high conductivity carbon material and the binder. The weight ratio is determined experimentally. If the weight ratio is less than the above-mentioned range, there is a problem that pores are formed too little and the surface resistance is not reduced. If the weight ratio is exceeded, the viscosity becomes too high, The polymer-containing coating layer may be detached.

The high specific surface area carbon material may be 25 to 80 wt%, the high conductivity carbon material may be 15 to 70 wt%, and the binder may be 1 to 40 wt%. If the weight ratio of the binder in the weight ratio is less than the specified weight ratio, there is a problem of falling off of the active material. If the weight ratio of the binder is less than the specified weight ratio, the electrolyte may not permeate through the carbon coating layer.

The water-soluble polymer is not limited as long as it dissolves well in a polar solvent such as water, ethanol and the like. However, the polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl pyrrolidone PVP). ≪ / RTI > Since the size of the water-soluble polymer determines the size of the pores formed in the carbon layer, the size of the water-soluble polymer can be determined in consideration of electrical characteristics such as fluidity of the electrolyte. In one embodiment, the size of the water- Lt; / RTI > If the size of the pores formed in the carbon layer is less than 0.1 m, there is a problem that the electrolyte penetrates through the pore formation. In the case where the pore size exceeds 100 m, the surface area of the water-soluble polymer-containing coating layer may decrease. Also, the water-soluble polymer should be mixed with the carbon material so that it can be used in a mixed state with the solvent.

The high specific surface area carbon material may be a carbon material having a specific surface area of 500 to 3,000 m ² / g. If the specific surface area of the high specific surface area carbon material is less than 500 m ² / g, There is a problem in that the electrode performance is deteriorated because it is not penetrated into the inside, and hydrogen generation is promoted due to excessive specific surface area exceeding 3,000 m ² / g, so that the reduction of the electrolyte becomes extreme and the life of the electrode is reduced. The high specific surface area carbon material used in the present invention may be any of known carbon materials as long as it is within the specific surface area described above, and may be activated carbon, carbon black, acetylene black or a combination thereof in one embodiment. If the size of the high specific surface area carbon material is less than 0.1 mu m, the scattering of the carbon material causes the stability of the working process to be very low, and the electrode layer having a size of more than 100 mu m Since uniform mixing is not achieved in constituting the slurry to be formed.

The highly conductive carbon material may be a carbon material having an electric conductivity of 20 S / m or more. If the electric conductivity of the highly conductive carbon material is less than 20 S / m, the electric conductivity of the carbon active material decreases, to be. The highly conductive carbon material used in the present invention may be any known carbon material as long as it is in the range of the above-mentioned electric conductivity, in one embodiment may be graphite, graphene, carbon nanotube or a combination thereof . Highly Conductive Carbon Material Powders of the same size as the high specific surface area carbon material may also be used.

The binder may be any known polymeric material for the binder, and may be at least one selected from the group consisting of, for example, polyester, PET, PTFE, PVdF, and CMC. Particularly, since the binder must be uniformly mixed with the carbon material, it can be used in a mixed state with the solvent.

The water-soluble polymer-containing carbon layer can be formed by dip coating on the electrode after preparing the electrode coating slurry containing the above-mentioned components. The water-soluble polymer contained in the electrode coating slurry is dissolved in the slurry solution in the slurry state After coating on the electrode, it is dried in the coating layer on the electrode surface and crystallized again. When the electrode thus manufactured is assembled together with the anode to form a unit cell, the porous electrode can be realized in which the electrode is in contact with the electrolytic solution to dissolve the water-soluble polymer in the electrolytic solution, thereby forming pores as large as the crystal size of the aqueous polymer. At this time, the thickness of the water-soluble polymer-containing carbon layer coated on the electrode may be 10 to 500 탆. If the thickness is less than 10 탆, meaningful performance of the carbon coating can not be expected. If the thickness is 500 탆 or more, This is because the surface of the electrode is clogged and the electrode performance may deteriorate.

In one embodiment, the lead-acid battery electrode of the present invention is produced by preparing a slurry for electrode coating with a water-soluble polymer-containing carbon layer slurry, dip coating the lead electrode slurry in an electrode coating slurry, For 0.5 to 10 hours for drying to obtain a water soluble polymer-containing carbon layer. The slurry for electrode coating may include a carbon material (including a weight ratio of activated carbon and graphite of 1: 1), a binder, and a water-soluble polymer solution. In one embodiment, 90 wt% carbon material and 10 wt% As a solid, a water-soluble polymer solution containing 10% by weight of a water-soluble polymer in distilled water as a solvent was mixed together to prepare a water-soluble polymer-containing carbon layer slurry so that the total solid concentration was 40% by weight.

The lead-acid based battery system of the present invention includes the electrode described above. That is, the electrode plate having the above-described structure may be implemented as a secondary battery including at least one of a cathode electrode and a cathode electrode. For example, the anode of the present invention may be used for both the anode and the cathode, It is possible to implement a secondary battery with a structure impregnated with sulfuric acid.

In particular, the lead-acid based battery system of the present invention can implement the above-described electrode as a cathode.

Example 1

1. Preparation of carbon materials

Activated carbon as high specific surface area carbon and graphite as high electric conductivity carbon were selected, and activated carbon and graphite were pulverized to prepare powders having a size of 10-30 탆.

2. Water-Soluble Polymer Preparation

PVA was selected as a water-soluble polymer and dissolved in water to prepare a 10 wt% solution.

3. Slurry preparation for electrode coating

90% by weight of carbon material (including graphite in a weight ratio of 1: 1) and 10% by weight of CMC as a binder were mixed with a water-soluble polymer solution containing 10% by weight of distilled water as a solvent, A slurry for electrode coating was prepared so that the total solid concentration was 40 wt%.

4. Formation of water-soluble polymer-containing carbon layer

An electrode having a water-soluble polymer-containing carbon layer having a thickness of 50 占 퐉 was prepared through dip coating using a slurry for electrode coating on a fused electrode plate.

Example 2

The electrode obtained in Example 1 was used as a cathode electrode, fixed to a case using a positive electrode and a separator, and impregnated with a sulfuric acid solution having a specific gravity of 1.3 to prepare a unit cell.

Comparative Example 1

A comparative electrode was prepared in the same manner as in Example 1, except that the water-soluble polymer was not added.

Comparative Example 2

A comparative unit cell was prepared in the same manner as in Example 2, except that the comparative anode was used as the cathode electrode.

Experimental Example 1

The capacities of the unit cells obtained in Example 2 and Comparative Example 2 and the comparative unit cells were evaluated as follows, and the results are shown in FIG.

The capacity was evaluated by charging until it reached 2.45 V with a current of 0.1 C (10 hour current), leaving it for 10 minutes for voltage and temperature stabilization, then discharging at a current of 0.1 C until reaching 1.75 V Respectively.

FIG. 1 shows only the results of the discharge. As shown in FIG. 1, the capacity of the unit cell including the electrode obtained according to the present invention is improved.

Experimental Example 2

The life of the unit cells obtained in Example 2 and Comparative Example 2 and the unit cells of Comparative Example were evaluated as follows, and the results are shown in Fig.

The life cycle is evaluated by charging each unit cell at a current of 0.1 C and charging it at 0.5 C (2 hour current) for 61 seconds. The discharge for 60 seconds was repeated at 0.5C. The cycle was terminated when the discharge end voltage reached 1.2V.

As shown in FIG. 2, it was confirmed that the lifetime of the unit cell including the electrode obtained in the present invention was remarkably improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, Various changes and modifications will be possible.

Claims (13)

1. An electrode support composed of lead; And

   And a water soluble polymer-containing carbon layer formed on the surface of the support.
2. The method according to claim 1,

   Wherein the water soluble polymer-containing carbon layer comprises a high specific surface area carbon material, a high conductivity carbon material, a water soluble polymer, and a binder.
3. 3. The method of claim 2,

   Wherein the water soluble polymer is contained in an amount of 1 to 30 parts by weight per 100 parts by weight of the sum of the high specific surface area carbon material, the high conductivity carbon material and the binder.
4. The method of claim 3,

   Wherein the high specific surface area carbon material, the high conductivity carbon material, and the binder are contained in an amount of 25 to 80 wt%, 15 to 70 wt%, and 1 to 40 wt%, respectively, in the total content.
5. The method according to claim 1,

   Wherein the water-soluble polymer has a size of 0.1 μm to 100 μm.
6. 6. The method according to any one of claims 1 to 5,

   Wherein the high specific surface area carbon material has a specific surface area of 500 to 3,000 m ² / g.
7. 6. The method according to any one of claims 1 to 5,

   Wherein the high conductivity carbon material has an electric conductivity of 20 S / m or more.
8. 6. The method according to any one of claims 1 to 5,

   Wherein the binder is at least one selected from the group consisting of polyester, PET, PTFE, PVdF, and CMC.
9. 6. The method according to any one of claims 1 to 5,

   Wherein the water soluble polymer is at least one selected from the group consisting of polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyvinyl pyrrolidone (PVP) Electrodes for lead acid batteries.
10. 6. The method according to any one of claims 1 to 5,

    Wherein the water soluble polymer-containing carbon layer is formed to a thickness of 10 탆 to 500 탆.
11. 6. The method according to any one of claims 1 to 5,

    Wherein the water soluble polymer-containing carbon layer dissolves in contact with the electrolytic solution to form pores.
12. A lead-acid based battery system comprising the electrode of any one of claims 1 to 5.
13. 13. The method of claim 12,

    Wherein the electrode is a negative electrode.

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