CN109314246B - Lead storage battery and method for measuring dissolution rate of lead sulfate - Google Patents

Lead storage battery and method for measuring dissolution rate of lead sulfate Download PDF

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CN109314246B
CN109314246B CN201780036754.4A CN201780036754A CN109314246B CN 109314246 B CN109314246 B CN 109314246B CN 201780036754 A CN201780036754 A CN 201780036754A CN 109314246 B CN109314246 B CN 109314246B
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lead sulfate
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浜野泰如
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GS Yuasa International Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/08—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
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    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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Abstract

A lead storage battery, wherein a negative electrode plate comprises a negative electrode material containing 0.2 mass% or more of barium sulfate and 0.05 mass% or more of a synthetic shrink-proofing agent, and the concentration of sulfur in the synthetic shrink-proofing agent is 4000 [ mu ] mol/g or more.

Description

Lead storage battery and method for measuring dissolution rate of lead sulfate
Technical Field
The present invention relates to a lead-acid battery and a method for measuring the dissolution rate of lead sulfate.
Background
The negative electrode material of the lead storage battery contains an organic shrinkage inhibitor such as lignin. In contrast, patent document 1(JP2013-41848) discloses a formaldehyde condensate containing a bisphenol a aminobenzenesulfonic acid sodium salt represented by the chemical structural formula [ chemical formula 1], the sulfur content in the compound being 6 to 10 mass%.
The charging of the lead storage battery is related to the dissolution reaction of lead sulfate which is decomposed into lead ions and sulfate ions and dissolved in the electrolyte. However, the dissolution rate of lead sulfate was not measured, and details of the dissolution reaction of lead sulfate related to charging, the reduction reaction of lead ions by the supply of electrons to the metal lead, the rate of discharge of sulfate ions from the voids, and the like were not known. Therefore, it is not known to what degree the dissolution reaction of lead sulfate has in the charging reaction.
Documents of the prior art
Patent document
Patent document 1: JP2013-41848
Disclosure of Invention
The inventors succeeded in measuring the dissolution rate of lead sulfate from the negative electrode plate, which has not been measured so far, and found that the dissolution reaction of lead sulfate is an important factor in determining the charging current. Further, a method of increasing the dissolution rate of lead sulfate was found.
The invention provides a lead storage battery with high regenerative charge acceptance performance and less lead sulfate accumulation.
Another object of the present invention is to provide a method for measuring the dissolution rate of lead sulfate.
One aspect of the present invention is a lead-acid battery, wherein the negative electrode plate comprises a negative electrode material containing 0.2 mass% or more of barium sulfate and 0.05 mass% or more of a synthetic shrinkage-preventing agent, and the sulfur concentration in the synthetic shrinkage-preventing agent is 4000 μmol/g or more. This improves the charge acceptance performance and suppresses the accumulation of lead sulfate.
In addition, one aspect of the present invention is a lead-acid battery, wherein the negative electrode plate comprises a negative electrode material containing at least 0.05 mass% of a synthetic shrinkproof agent and having a sulfur content of 0.2mg/cm3The above. This improves the charge acceptance performance and suppresses the accumulation of lead sulfate.
One aspect of the present invention is a lead-acid battery, wherein a negative electrode plate comprises a negative electrode material, and is discharged from a fully charged state at 25 ℃ for 30 minutes at a constant current of 0.2CA, and after leaving for 15 minutes, the negative electrode is set to have a potential corresponding to Pb | PbSO4(sulfuric acid having a specific gravity of 1.30 at 25 ℃) in a state where the electrode was charged at-300 mV, the charging current flowing during 20 minutes of charging was measured, and the dissolution rate of lead sulfate from the negative electrode plate at 25 ℃ was 1.0X 10 by the nonlinear least squares method using numerical expressions 1 to 3-8mol s-1cm-2The above. If the dissolution rate of lead sulfate is 1.0X 10-8mol s- 1cm-2As described above, the charge acceptance is improved, and the accumulation of lead sulfate can be suppressed.
[ mathematical formula 1]
Figure GDA0003062226840000021
[ mathematical formula 2]
Figure GDA0003062226840000022
Time of flight
Figure GDA0003062226840000023
Figure GDA0003062226840000024
Time of flight
Figure GDA0003062226840000025
[ mathematical formula 3]
Figure GDA0003062226840000026
i (t) is the charging current value of the t second from the particle size before charging of l0Number of lead sulfates N (l)0) With current i of each10The product of (t) is shown. z, F, M and rho are respectively the charge number, Faraday constant, molecular weight of lead sulfate, density of lead sulfate, k and lmAnd α are the dissolution rate of lead sulfate and the size and shape parameters that determine the particle size distribution, respectively. In the present invention, it is assumed that the charging reaction of the negative electrode proceeds by a dissolution and precipitation mechanism. The inventors have also found that the charging current can be analyzed by using a pareto distribution of the particle sizes of lead sulfate, and that the dissolution rate of lead sulfate can be measured.
[ Table 1]
TABLE 1 summary of the parameters
Figure GDA0003062226840000031
One of the present invention is a method for measuring a dissolution rate of lead sulfate, in which 0.2CA is performed for 30 minutes for a fully charged lead-acid batteryConstant current discharge, and after leaving for 15 minutes, the potential of the negative electrode was adjusted to Pb | PbSO4The charging current flowing during 20 minutes of charging was measured in a state where the electrode was at-300 mV (sulfuric acid having a specific gravity of 1.30 at 25 ℃), and the dissolution rate of lead sulfate was measured by the nonlinear least squares method using numerical expressions 1 to 3. Thus, the dissolution rate of lead sulfate can be measured, and the characteristics of the lead-acid battery can be evaluated by using the dissolution rate. These inventions are each one of the inventions, and need not be all satisfied.
[ mathematical formula 1]
Figure GDA0003062226840000032
[ mathematical formula 2]
Figure GDA0003062226840000041
Time of flight
Figure GDA0003062226840000042
Figure GDA0003062226840000043
Time of flight
Figure GDA0003062226840000044
[ mathematical formula 3]
Figure GDA0003062226840000045
[ Table 1]
TABLE 1 summary of the parameters
Figure GDA0003062226840000046
Drawings
Fig. 1 is a characteristic diagram showing a relationship between the regenerative charging receptivity and the barium sulfate content.
FIG. 2 is a characteristic diagram showing the relationship between the regenerative charging receptivity and the sulfur content of the synthetic shrinkproof agent.
FIG. 3 is a characteristic diagram showing the relationship between the regenerative charging receptivity and the content of the synthetic shrinkproof agent.
FIG. 4 is a characteristic diagram showing the relationship between the PSoC cycle life and the barium sulfate content.
FIG. 5 is a characteristic diagram showing the relationship between the PSoC cycle life and the sulfur content of the synthetic shrinkproof agent.
FIG. 6 is a characteristic diagram showing the relationship between the PSoC cycle life and the content of the synthetic shrinkproof agent.
FIG. 7 is a characteristic diagram showing the relationship between the lead sulfate accumulation amount and the barium sulfate content.
FIG. 8 is a characteristic diagram showing the relationship between the lead sulfate accumulation amount and the sulfur content of the synthetic shrinkproof agent.
FIG. 9 is a characteristic diagram showing the relationship between the lead sulfate accumulation amount and the synthetic shrinkproof agent content.
Fig. 10 is a characteristic diagram showing the relationship between the PSoC cycle life and the dissolution rate of lead sulfate.
Fig. 11 is a characteristic diagram showing a relationship between the plate thickness and the dissolution rate of lead sulfate.
Fig. 12 is a characteristic diagram showing a relationship between the elemental sulfur content per volume of the active material and the regenerative charging acceptance performance.
Detailed Description
One embodiment of the present invention is a lead-acid battery, wherein the negative electrode plate comprises a negative electrode material, the negative electrode material contains 0.2 mass% or more of barium sulfate and 0.05 mass% or more of a synthetic shrinkage inhibitor, and the sulfur concentration in the synthetic shrinkage inhibitor is 4000 μmol/g or more. This improves the charge acceptance and suppresses the accumulation of lead sulfate.
In addition, one embodiment of the present invention is a lead-acid battery, wherein the negative electrode plate comprises a negative electrode material containing 0.05 mass% or more of a synthetic shrinkage inhibitor, and the sulfur content of the negative electrode material is 0.2mg/cm3The above. Thereby, the charge acceptance performance is improved,and can suppress the accumulation of lead sulfate.
Here, the negative electrode material may contain 0.2 mass% or more of barium sulfate. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
The concentration of the sulfur element in the synthetic shrinkproof agent may be 6000. mu. mol/g or less. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
One embodiment of the present invention is a lead-acid battery, wherein the negative electrode plate comprises a negative electrode material, and is discharged from a fully charged state at 25 ℃ for 30 minutes at a constant current of 0.2CA, and after leaving for 15 minutes, the negative electrode is set to have a potential corresponding to Pb | PbSO4(sulfuric acid having a specific gravity of 1.30 at 25 ℃) in a state where the electrode was charged at-300 mV, the charging current flowing during 20 minutes of charging was measured, and the dissolution rate of lead sulfate from the negative electrode plate at 25 ℃ was 1.0X 10 by the nonlinear least squares method using numerical expressions 1 to 3-8mol s-1cm-2The above. Thus, if the dissolution rate of lead sulfate is 1.0X 10-8mol s-1cm-2As described above, the charge acceptance is improved, and the accumulation of lead sulfate can be suppressed.
Here, the negative electrode material may contain 0.2 mass% or more of barium sulfate. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
Here, the negative electrode material may contain 0.05 mass% or more of a synthetic shrink proofing agent. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
The negative electrode material may contain a synthetic shrink inhibitor, and the sulfur concentration in the synthetic shrink inhibitor may be 4000. mu. mol/g or more. Thus, the dissolution rate of lead sulfate at 25 ℃ can be set to 1.0X 10-8mol s-1cm-2The above.
Here, the thickness of the negative electrode plate can be set to 1.0mm or more, whereby the dissolution rate of lead sulfate increases, and as a result, the regenerative charging acceptance performance can be improved and the effect of preventing accumulation of lead sulfate can be obtained.
One embodiment of the present invention is a method for measuring a dissolution rate of lead sulfate, in which a fully charged lead-acid battery is subjected to constant current discharge of 0.2CA for 30 minutes, left for 15 minutes, and then the potential of the negative electrode is adjusted to Pb | PbSO4The charging current flowing during 20 minutes of charging was measured in a state where the electrode was at-300 mV (sulfuric acid having a specific gravity of 1.30 at 25 ℃), and the dissolution rate of lead sulfate was measured by the nonlinear least squares method using numerical expressions 1 to 3. Thus, the dissolution rate of lead sulfate can be measured, and the characteristics of the lead-acid battery can be evaluated by using the dissolution rate.
1 if the negative electrode material contains 0.2 mass% or more of barium sulfate, the improvement of the regenerative charge acceptance and the lead sulfate accumulation prevention effect become remarkable.
2 if the negative electrode material contains 2.0 mass% or less of barium sulfate, the improvement of the regenerative charge acceptance and the effect of preventing the accumulation of lead sulfate become remarkable.
3 if the negative electrode material contains 0.2 mass% or more of the synthetic shrinkage-preventing agent, the improvement of the regenerative charging acceptance and the effect of preventing the accumulation of lead sulfate become remarkable.
4 if the negative electrode material contains 0.8 mass% or less of the synthetic anti-shrinkage agent, the improvement of the regenerative charging acceptance and the effect of preventing the accumulation of lead sulfate become remarkable.
5 the negative electrode material contains 0.2-2.0 mass% of barium sulfate and 0.05-0.8 mass% of synthetic shrink-proof agent, and the concentration of sulfur element in the synthetic shrink-proof agent is 4000-6000 mu mol/g. Thus, the improvement of the regenerative charging acceptance performance and the effect of preventing the accumulation of lead sulfate are more excellent than those obtained when the barium sulfate content is not 0.2 to 2.0 mass%, the synthetic shrinkproof agent content is 0.05 to 0.8 mass%, and the sulfur element concentration in the synthetic shrinkproof agent is 4000 to 6000. mu. mol/g.
6 dissolution rate of lead sulfate at 25 ℃ of 1.0×10-8mol s-1cm-2In the above negative electrode plate, if the negative electrode material contains 0.2 mass% or more of barium sulfate, the improvement of the regenerative charge acceptance and the prevention and suppression effect of the accumulation of lead sulfate are easily obtained.
7 the dissolution rate of lead sulfate at 25 ℃ is 1.0X 10-8mol s-1cm-2In the above negative electrode plate, if the negative electrode material contains the synthetic shrinkproof agent in an amount of 0.05 mass% or more, the improvement of the regenerative charging acceptance and the effect of preventing the accumulation of lead sulfate can be easily obtained.
The dissolution rate of lead sulfate at 25 ℃ of 8 was 1.0X 10-8mol s-1cm-2In the above negative electrode plate, if the negative electrode material contains the synthetic shrinkproof agent and the sulfur concentration in the synthetic shrinkproof agent is 4000. mu. mol/g or more, the improvement of the regenerative charging acceptance performance and the inhibition effect of the accumulation of lead sulfate can be obtained.
9 if the thickness of the negative electrode plate is 1.0mm or more, the dissolution rate of lead sulfate increases, and as a result, the regenerative charging acceptance performance is improved and the effect of preventing accumulation of lead sulfate is obtained.
In the examples, bisphenol sulfonic acid formaldehyde condensates were used as the synthetic shrinkproof agent. However, the same results were obtained with other synthetic shrinkproof agents such as naphthalene sulfonic acid formaldehyde condensate. The S element may contain a sulfonyl group or the like in addition to the sulfonic acid group, and the S element may be present in any form. The bisphenol may be any of A-type, F-type and S-type. The condensing agent is, for example, formaldehyde in the case of bisphenol sulfonic acid or naphthalene sulfonic acid, but the type of the condensing agent is arbitrary. The sulfonic acid group may be directly bonded to a phenyl group of bisphenol or a naphthyl group of naphthalenesulfonic acid, or may be bonded to another phenyl group, naphthyl group, alkyl group, or the like different from bone lattice.
Method for measuring dissolution rate of lead sulfate
Drilling holes in each cell of the cover of the lead storage battery, and connecting Pb | PbSO of the reference electrode4Electrodes (immersed in sulfuric acid with a specific gravity of 1.30 at 25 ℃). After the battery is fully chargedAnd is placed at 25 deg.c. Then, the mixture was discharged at 25 ℃ for 30 minutes at 0.2CA (6.8A), left for 15 minutes, and then charged. The charge was a constant voltage charge, and the charge was performed so that the unipolar potential of the negative electrode of any one of the battery cells became a voltage of-300 mV with respect to the reference electrode. In this case, the voltage may be manually controlled or a potentiostat may be used. In addition, a Cd electrode or Hg | Hg electrode can be used as a reference electrode2SO4Electrodes, and the like. The charge was carried out for 20 minutes and the current at this time was recorded. The dissolution rate of lead sulfate can be measured by matching the current with the following theoretical formula by the nonlinear least square method. This measurement is performed in a lead-acid battery, and it is not necessary to take out a negative electrode plate or a negative electrode active material from the lead-acid battery. In other words, measurement that accurately reflects the charging reaction of the lead storage battery can be performed.
The parameters used for the measurement of the dissolution rate are those shown in table 1. The lead sulfate particles were formed into a nearly cubic shape, and the size was specified by the length of one side. In Table 1, the probability distribution P (l)0) Related dimension parameter lmThe minimum particle diameter of the lead sulfate particles was 5X 10－5cm (0.5 μm). The mathematical formula 3 represents a probability distribution of the size of the lead sulfate particles, and the number of lead sulfate particles of a certain size is proportional to the inverse of the power of α +1 of the size. Equation 3 holds when t is 0, and the unknown number is the total particle number NTotal ofAnd a shape parameter alpha. Mathematical formula 2 represents a size of l for lead sulfate particles0The dissolution current of one particle. The total dissolution current is expressed by equation 1, and if equation 2 and equation 3 are added, the unknown number is NTotal ofThe initial values of (a), the shape parameter α and the dissolution rate k of lead sulfate, these 3 parameters can be determined by the nonlinear least squares method.
It is known that the charge reaction of the negative electrode plate in the charging of the lead-acid battery is a rate-limiting stage. This analysis of the limiting current when the charging voltage was changed confirmed for the first time that the dissolution reaction of lead sulfate was the slowest reaction in the reduction process of lead sulfate. Further, it was confirmed that the dissolution rate of lead sulfate is determined by a value specific to the design of the lead storage battery, and the reduction current and the dissolution rate of lead sulfate have a relationship of formula 1. When the reduction processes in sulfuric acid are compared in the negative electrodes of different batteries, if the comparison is made only with the magnitude of the charging current, the magnitude relationship changes greatly depending on the time from the start of charging, and sometimes the inversion occurs. Therefore, it is impossible to determine whether or not the battery is designed to be less likely to retain lead sulfate, based on only the magnitude of the charging current. Therefore, it was found that the dissolution rate of lead sulfate can be determined by using the relationship shown in equation 1. It has also been found that the charging characteristics of lead storage batteries are determined by the dissolution rate of lead sulfate.
Evaluation of regeneration acceptance Property
At 25 ℃, charging was started from a state of charge (SOC) of 90% under the conditions of a charging voltage of 14.4V and a limiting current of 100A, and the charge capacity for the first 5 seconds was measured as the regenerative charging acceptance.
SBA-IS Life test
The IS life test IS defined by SBA S0101: 2006, and the following cycles are repeated while standing for 40-48 hours every 3600 cycles in a 25 ℃ gas tank: after discharging at a constant current of 45A for 59 seconds and pulse discharging at 300A for 1 second, the resultant was charged at a constant voltage of 14V for 60 seconds at a maximum current of 100A. Then, if the discharge voltage at the time of pulse discharge of 300A for 1 second is less than 7.2V, the life is determined. The negative electrode plate was taken out of the lead-acid battery having reached the end of its life, and the amount of lead sulfate accumulated was measured.
Quantification of organic shrink-proofing agent
The kind of the organic shrinkproof agent in the negative electrode active material was determined in the following manner. The fully charged lead-acid battery is decomposed, and the negative electrode plate is taken out, washed with water to remove sulfuric acid components, and dried. The active material was separated from the negative electrode plate, and the active material was immersed in a 1mol/l aqueous solution of NaOH to extract the organic shrinkproof agent, and the solution from which insoluble components were removed by filtration was desalted, concentrated and dried to obtain a powder sample. Diluting the powder sample by using distilled water, and determining the type of the organic shrink-proof agent by using an ultraviolet-visible absorption spectrum obtained by an ultraviolet-visible absorption photometer. When the ultraviolet-visible light absorption spectrum is insufficient, a powder sample obtained by concentration and drying may be separately prepared, and other analytical instruments capable of analyzing the structure, such as infrared spectroscopy (IR) and NMR, may be used.
The content of the organic shrinkproof agent in the negative electrode active material was measured in the following manner. The fully charged lead-acid battery was decomposed, and the negative electrode plate was taken out, washed with water to remove the sulfuric acid component, and dried. The active material was separated from the negative electrode plate, 100g of the active material was immersed in 300ml of a 1mol/l aqueous NaOH solution to extract an organic shrinkproof agent, insoluble components in the solution were removed by filtration, and then the ultraviolet-visible absorption spectrum was measured, and the content of the organic shrinkproof agent in the active material was measured using a calibration curve prepared in advance. When the battery is obtained and the content of the synthetic shrinkproof agent is measured, since the structural formula of the organic shrinkproof agent cannot be accurately determined, when the same organic shrinkproof agent cannot be used for the calibration curve, the following procedure can be performed. In the measurement methods of ultraviolet-visible absorption spectrum, infrared spectrum, NMR spectrum, and the like, an organic shrink preventing agent that is additionally available, showing a shape similar to that of the organic shrink preventing agent extracted from the negative electrode of the battery, is selected. And (3) preparing a calibration curve of the ultraviolet-visible absorption spectrum by using the selected organic shrink-proof agent, and measuring the content of the organic shrink-proof agent in the battery.
The S element content of the organic anti-shrinkage agent in the negative electrode active material (hereinafter simply referred to as "S element content") was measured in the following manner. The fully charged lead-acid battery is decomposed, and the negative electrode plate is taken out, washed with water to remove sulfuric acid, and dried. The active material was separated from the negative electrode plate, and the active material was immersed in a 1mol/l aqueous solution of NaOH to extract the organic shrinkproof agent, and the solution from which insoluble components were removed by filtration was desalted, concentrated and dried to obtain a powder sample. The S element in 0.1g of the organic shrinkproof agent was converted to sulfuric acid by the oxygen bottle combustion method, and the content of the S element in the organic shrinkproof agent was determined by titrating the dissolution liquid with barium perchlorate using thorium reagent as an indicator.
3Method for measuring content (mg/cm) of synthetic shrink-proof agent
The density of the negative electrode material was measured in the following manner. The chemically converted anode active material in a fully charged state was washed with water and dried, and the apparent volume v per 1g and the total pore volume u per 1g were measured by mercury intrusion in an unground state. Note that the apparent volume v is the sum of the solid volume of the negative electrode material and the volume of the closed pores.
A negative electrode material having a mass a was charged into a container having a known volume V1, and the pore diameter was measured by mercury intrusion measurement to be equivalent to a volume V2 of 100 μm or more. The mercury was continuously introduced and the total pore volume u was measured.
The density d of the negative electrode material was determined by assuming (V1-V2)/a-u as the apparent volume V and d as 1/(V + u) as a/(V1-V2).
The sulfur element content S of the negative electrode material was determined as S ═ Mecd from the measured content c of the synthetic shrinkproof agent and the amount e of the synthetic shrinkproof agent. In addition, M represents the atomic weight of sulfur.
Quantification of barium sulfate
10g of the negative electrode active material washed and dried with water was pulverized, 50mL of the pulverized material was dissolved with heating using 1:2 nitric acid (concentrated nitric acid was mixed with water at a volume ratio of 1: 2), and a supersaturated aqueous ammonium acetate solution was added thereto in a large excess amount and stirred to completely dissolve lead sulfate. The solution was subjected to suction filtration using a membrane filter having a pore size of 0.1 μm (パス), and the residue was dried and then heated at 700 ℃ to be ashed. By heating to 700 ℃, only barium oxide remained, and weighed and converted to barium sulfate.
The following shows preferred embodiments of the invention of the present application. In carrying out the invention of the present application, the embodiments may be appropriately modified based on common general knowledge of those skilled in the art and disclosure of the prior art. In the examples, the negative electrode material is sometimes referred to as a negative electrode active material, and the positive electrode material is sometimes referred to as a positive electrode active material. The negative electrode plate is composed of a negative electrode current collector (negative electrode grid) and a negative electrode material (negative electrode active material), the positive electrode plate is composed of a positive electrode current collector (positive electrode grid) and a positive electrode material (positive electrode active material), and the solid components other than the current collector are the electrode materials.
Production example of lead acid Battery
Bisphenol sulfonic acid formaldehyde condensates were used as synthetic shrink inhibitors. Lead powder, a synthetic shrinkproof agent, carbon, barium sulfate and a synthetic fiber reinforcing material are mixed by water and sulfuric acid to prepare a negative electrode active material paste. The negative electrode active material (strictly speaking, the negative electrode material) after the chemical conversion contained 0.3 mass% of carbon and 0.1 mass% of a synthetic fiber reinforcing material, but the contents of carbon and the synthetic fiber reinforcing material were arbitrary. The negative electrode active material paste is filled into a negative electrode grid made of a Pb-Ca-Sn alloy, and dried and cured to produce a non-chemically converted negative electrode plate. The kind of lead powder, production conditions, the kind of grid, and the like are arbitrary, and the negative electrode active material may contain components other than those described above.
Lead powder and a synthetic fiber reinforcement (0.1 mass% with respect to the chemically converted positive electrode active material) were kneaded with water and sulfuric acid to prepare a positive electrode active material paste. The paste was filled into a positive electrode grid made of a Pb-Ca-Sn alloy, and dried and cured to obtain a positive electrode plate which was not chemically converted.
The non-chemically transformed negative electrode plate was housed in a bag-shaped separator made of microporous polyethylene, and the non-chemically transformed positive electrode plate 5 and the non-chemically transformed negative electrode plate 6 of each cell were placed in a battery container so as to face each other, and the battery container was chemically transformed by adding an electrolyte solution, thereby producing a 44B20 type flooded lead acid battery. The thickness of the negative electrode plate after chemical conversion, that is, the thickness of the negative electrode active material, is changed within a range of 1.0mm to 1.8mm, and if it exceeds 1.6mm, there is a problem that the gap between the electrode plates is too narrow. The lead acid battery may be a valve regulated type, and an Sb alloy or the like may be used as the current collector of the positive electrode of the plug instead of the grid.
Results
The results are shown in table 2, table 3 and fig. 1 to 12. The regenerative charging receptivity, the PSoC cycle life, and the amount of lead sulfate accumulated after the PSoC cycle are represented by relative values with sample No.1 in Table 2 being 100%. The organic shrinkproof agent having an S element content of 600. mu. mol/g in terms of the unit such as content is lignin, and the other is a synthetic shrinkproof agent.
[ Table 2]
TABLE 2 summary of measurement results
Figure GDA0003062226840000121
[ Table 3]
TABLE 3 measurement results
Figure GDA0003062226840000131
As shown in FIGS. 1 and 2, when the barium sulfate content is 0.2 to 2.0 mass% and the sulfur content of the synthetic shrinkproof agent is 4000. mu. mol/g or more, high regenerative charging receptivity can be obtained. As shown in fig. 3, when the content of the synthetic shrinkproof agent in the negative electrode active material is 0.05 mass% or more, particularly 0.2 to 0.8 mass%, and the content of the sulfur element in the synthetic shrinkproof agent is 4000 μmol/g or more, high regenerative charging receptivity can be obtained.
As shown in FIGS. 4 and 5, when the barium sulfate content is 0.2 to 2.0 mass% and the sulfur content of the synthetic shrinkproof agent is 4000. mu. mol/g or more, a high PSoC cycle life can be obtained. As shown in fig. 6, when the content of the synthetic shrinkproof agent in the negative electrode active material is 0.05 mass% or more, particularly 0.2 to 0.8 mass%, and the content of the sulfur element in the synthetic shrinkproof agent is 4000 μmol/g or more, a high PSoC cycle life can be obtained.
The amount of lead sulfate accumulated in the negative electrode after the PSoC cycle life is small if the PSoC cycle life is long, and the amount of lead sulfate accumulated in the negative electrode after the PSoC cycle life is large if the PSoC cycle life is short. As shown in FIGS. 7 and 8, when the barium sulfate content is 0.2 to 2.0 mass% and the sulfur content of the synthetic shrinkproof agent is 4000. mu. mol/g or more, the amount of lead sulfate accumulated is small. As shown in fig. 9, when the content of the synthetic shrinkproof agent in the negative electrode active material is 0.05 mass% or more, particularly 0.2 to 0.8 mass%, and the content of sulfur element in the synthetic shrinkproof agent is 4000 μmol/g or more, the amount of lead sulfate accumulated is small.
FIG. 10 shows the relationship between the dissolution rate of lead sulfate and the PSoC cycle life. By increasing the dissolution rate, the PSoC cycle life is extended. And if the dissolution rate is less than 1.0X 10-8mol s-1cm-2Then, as shown in the lower left corner of FIG. 10, the PSoC cycle life is centered at a low value, if it exceeds 1.0X 10-8mol s-1cm-2The cycle life is greatly increased.
As shown in table 2, by increasing the dissolution rate, the regenerative charging acceptance was improved, and the amount of lead sulfate accumulated after the PSoC cycle was decreased. The dissolution rate of any one of the regenerative charging receptivity, the PSoC cycle life and the lead sulfate accumulation amount after the PSoC cycle is less than 1.0X 10-8mol s-1cm-2And a dissolution rate of 1.0X 10-8mol s-1cm-2In the above, the lead storage batteries are divided into different groups. This means that the dissolution rate was 1.0X 10-8mol s-1cm-2The above is significant, and is preferably 1.8X 10-8mol s-1cm-2Above, most preferably 2.0X 10-8mol s-1cm-2The above. In table 2, the dissolution rate of lead sulfate was changed by 20 times at the maximum, but the regenerative charging acceptance was increased by only about 80% at the maximum. It is inferred that this is caused by the maximum current in regenerative charging being limited or the like.
Although data are not shown, the dissolution rate of lead sulfate is affected by factors other than the content of the synthetic shrinkproof agent and the content of elemental sulfur, and the content of barium sulfate. Therefore, even if the content of the synthetic shrinkproof agent and the content of elemental sulfur, and the content of barium sulfate are determined, the solubility of lead sulfate cannot be determined immediately. If the thickness of the negative electrode plate is increased or the ambient temperature is increased, the dissolution rate of lead sulfate increases. In addition, the content of sulfur per volume of the negative electrode active material (the amount of sulfur contained in the synthetic shrinkproof agent/volume of the negative electrode active material) also affects the content. On the other hand, if the density of the negative electrode active material is increased or the sulfuric acid concentration is increased, the dissolution rate decreases. In addition, sodium ions tend to decrease the dissolution rate due to the influence of sodium ions, lithium ions, aluminum ions, and the like in the electrolyte solution. This suggests the possibility that the dissolution reaction of lead sulfate is related to various factors of the lead storage battery and the mechanism of these factors can be clarified from the dissolution reaction rate of lead sulfate.
Fig. 11 shows the relationship between the thickness of the negative electrode plate and the dissolution rate of lead sulfate, with the density of the negative electrode active material being constant, and the dissolution rate increases if the plate is thickened. However, if the plate thickness is set to 1.8mm, the inter-electrode distance becomes too short, and therefore the negative plate thickness is preferably 1.0mm to 1.6 mm.
Table 3 and fig. 12 show the results when the sulfur content per volume of the negative electrode active material was changed. The content of barium sulfate was made constant, and the sulfur element content per volume of the negative electrode active material was changed by changing the sulfur element content of the synthetic shrinkage-preventing agent and the concentration of the synthetic shrinkage-preventing agent. The content of sulfur element in the negative electrode active material per volume was 0.2mg cm-3Above and less than 0.2mg cm-3The dissolution rate of lead sulfate, the regenerative charge acceptance, the life of the PSoC cycle, and the amount of lead sulfate accumulated after the PSoC cycle were divided into 2 groups.
The present invention can be implemented by the following means.
A lead-acid battery, wherein a negative electrode plate of the lead-acid battery comprises a negative electrode material containing 0.2 mass% or more of barium sulfate and 0.05 mass% or more of a synthetic shrinkage-preventing agent, and the sulfur concentration in the synthetic shrinkage-preventing agent is 4000 [ mu ] mol/g or more. This improves the regenerative charging acceptance and prevents the accumulation of lead sulfate.
A lead-acid battery, wherein the negative plate of the lead-acid battery comprises a negative electrode material containing 0.05 mass% or more of a synthetic shrinkproof agent containing sulfur, and the sulfur content of the negative electrode material is 0.2mg/cm3The above. This improves the regenerative charging acceptance and prevents the accumulation of lead sulfate.
3 in the lead-acid battery of mode 2, the negative electrode material contains 0.2 mass% or more of barium sulfate. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
4 in the lead-acid battery of the embodiment 1 or 2, the negative electrode material contains 2.0 mass% or less of barium sulfate. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
5 in the lead-acid battery of the embodiment 1 or 2, the negative electrode material contains 0.2 mass% or more of the synthetic shrinkage-preventing agent. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
6 in the lead-acid battery of the embodiment 1 or 2, the negative electrode material contains 0.8 mass% or less of the synthetic shrinkage inhibitor. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
7 in the lead-acid battery according to mode 1 or 2, the concentration of the sulfur element in the synthetic anti-shrinkage agent is 6000 μmol/g or less. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
8 in the lead-acid battery according to mode 1 or 2, the negative electrode material contains 0.2 to 2.0 mass% of barium sulfate and 0.05 to 0.8 mass% of a synthetic shrink-proofing agent, and the concentration of sulfur in the synthetic shrink-proofing agent is 4000 to 6000 μmol/g. This significantly improves the regenerative charging acceptance and significantly suppresses the accumulation of lead sulfate.
A lead-acid battery comprising a negative electrode plate having a negative electrode material, wherein the negative electrode plate is discharged from a fully charged state at 25 ℃ for 30 minutes at a constant current of 0.2CA, left for 15 minutes, and then the potential of the negative electrode is adjusted to Pb | PbSO4(sulfuric acid having a specific gravity of 1.30 at 25 ℃) in a state where the electrode was charged at-300 mV, the charging current flowing during 20 minutes of charging was measured, and the dissolution rate of lead sulfate from the negative electrode plate at 25 ℃ was 1.0X 10 by the nonlinear least squares method using numerical expressions 1 to 3-8mol s-1cm-2The above. By setting the dissolution rate of lead sulfate to 1.0X 10- 8mol s-1cm-2As described above, the improvement of the regenerative charging acceptance performance and the effect of preventing and suppressing the accumulation of lead sulfate become remarkable.
A method of measuring a dissolution rate of lead sulfate, comprising the steps of conducting constant current discharge of 0.2CA for 30 minutes to a fully charged lead-acid battery, leaving the battery for 15 minutes, and then setting the potential of the negative electrode to Pb | PbSO4The charging current flowing during 20 minutes of charging was measured in a state where the electrode was at-300 mV (sulfuric acid having a specific gravity of 1.30 at 25 ℃), and the dissolution rate of lead sulfate was measured by the nonlinear least squares method using numerical expressions 1 to 3. The characteristics of a lead-acid battery can be easily evaluated if the dissolution rate of lead sulfate can be measured.
11 the lead-acid battery according to mode 9, wherein the negative electrode material contains 0.2 mass% or more of barium sulfate.
12 in the lead-acid battery of mode 9, the negative electrode material contains 2.0 mass% or less of barium sulfate.
13 in the lead-acid battery of mode 9, the negative electrode material contains 0.05 mass% or more of the synthetic shrinkage-preventing agent.
14 in the lead-acid battery of mode 9, the negative electrode material contains 0.8 mass% or less of the synthetic shrinkage-preventing agent.
15 in the lead-acid battery of mode 9, the negative electrode material contains a synthetic shrinkage-preventing agent, and the concentration of sulfur in the synthetic shrinkage-preventing agent is 4000 μmol/g or more.
16 in the lead-acid battery of mode 9, the negative electrode material contains a synthetic shrinkage inhibitor, and the concentration of sulfur in the synthetic shrinkage inhibitor is 6000 μmol/g or less.
17 in the lead-acid battery of the mode 9 or 10, the negative electrode material contains 0.2 to 2.0 mass% of barium sulfate and 0.05 to 0.8 mass% of a synthetic shrinkage-preventing agent, and the concentration of sulfur element in the synthetic shrinkage-preventing agent is 4000 μmol/g or more. Thus, the dissolution rate of lead sulfate at 25 ℃ can be set to 1.0X 10-8mol s-1cm-2The above.
18-mode 1-9 or 11-17 lead-acid battery, wherein the thickness of the negative plate is 1.0mm or more.
19 in the lead-acid batteries of modes 1 to 9 or 11 to 17, the thickness of the negative electrode plate is 1.6mm or less.
20 in the lead-acid battery of modes 1 to 9 or 11 to 17, the thickness of the negative electrode plate is 1.0mm to 1.6 mm. This can further increase the dissolution rate of lead sulfate.
[ mathematical formula 1]
Figure GDA0003062226840000171
[ mathematical formula 2]
Figure GDA0003062226840000172
Time of flight
Figure GDA0003062226840000173
Figure GDA0003062226840000174
Time of flight
Figure GDA0003062226840000175
[ mathematical formula 3]
Figure GDA0003062226840000176
Wherein the parameters of the numerical expressions 1 to 3 are as defined in Table 1.
[ Table 1]
TABLE 1 summary of the parameters
Figure GDA0003062226840000177

Claims (10)

1. A lead storage battery, wherein the thickness of a negative plate is 1.0mm or more,
the negative electrode plate is provided with a negative electrode material,
the negative electrode material contains 0.2 mass% or more of barium sulfate and 0.05 mass% or more of a synthetic shrinkage-preventing agent,
and the concentration of sulfur element in the synthetic shrink-proof agent is more than 4000 mu mol/g.
2. A lead storage battery, wherein the thickness of a negative plate is 1.0mm or more,
the negative electrode plate is provided with a negative electrode material,
the negative electrode material contains more than 0.05 mass percent of synthetic shrink-proof agent, the synthetic shrink-proof agent contains sulfur element, and the sulfur element content of the negative electrode material is 0.2mg/cm3The above.
3. The lead-acid battery according to claim 2, wherein the negative electrode material contains 0.2 mass% or more of barium sulfate.
4. The lead-acid battery according to claim 1 or 2, wherein the concentration of elemental sulfur in the synthetic shrinkproof agent is 6000 μmol/g or less.
5. A lead-acid battery in which, among others,
has a negative plate and a negative plate,
the negative electrode plate is provided with a negative electrode material,
constant current discharge of 0.2CA was performed at 25 ℃ for 30 minutes from a fully charged state, and after leaving for 15 minutes, the potential of the negative electrode was adjusted to Pb | PbSO4Under the condition that the electrode has-300 mV, the charging current flowing during 20 minutes charging is measured, and the dissolution rate of the lead sulfate at 25 ℃ is 1.0X 10 by utilizing the mathematical formula 1 to the mathematical formula 3 and by the nonlinear least square method-8mol s-1cm-2In the above-mentioned manner,
the Pb | PbSO4The electrode was immersed in sulfuric acid having a specific gravity of 1.30 at 25 c,
[ mathematical formula 1]
Figure FDA0003062226830000011
[ mathematical formula 2]
Figure FDA0003062226830000021
Time of flight
Figure FDA0003062226830000022
Figure FDA0003062226830000023
Time of flight
Figure FDA0003062226830000024
[ mathematical formula 3]
Figure FDA0003062226830000025
Wherein, the unit and meaning of the parameter of the mathematical formula 1 to the mathematical formula 3 are as follows:
l is expressed in μm, and represents the length of one side of lead sulfate,
N(l0) Indicates a length of one side of l0The amount of lead sulphate in the lead-containing composition,
n in total represents the amount of total lead sulfate,
P(l0) Indicates a length of one side of l0The probability distribution of the number of lead sulfates,
lm in μm, representing P (l)0) The size parameter of (a) is,
the unit of alpha is mum and represents P (l)0) The shape parameter of (a) is,
i has the unit a, represents the current,
z represents a valence number, and z represents a valence number,
the unit of F is Cmol-1And the number of electrons representing the Faraday constant,
unit of kIs mol s-1cm-2The expression "indicates the dissolution rate of lead sulfate,
l0the unit of (d) is μm, and represents the length of one side of lead sulfate having t of 0,
m has the unit gmol-1It represents the molecular weight of lead sulfate,
rho is given in gcm-3And represents the density of lead sulfate.
6. The lead-acid battery according to claim 5, wherein the negative electrode material contains 0.2 mass% or more of barium sulfate.
7. The lead-acid battery according to claim 5, wherein the negative electrode material contains 0.05 mass% or more of a synthetic shrink-proofing agent.
8. The lead-acid battery according to claim 5, wherein the negative electrode material contains a synthetic shrinkproof agent, and the sulfur concentration in the synthetic shrinkproof agent is 4000. mu. mol/g or more.
9. The lead-acid battery according to any one of claims 5 to 8, wherein the negative electrode plate has a thickness of 1.0mm or more.
10. A method for measuring the dissolution rate of lead sulfate, wherein a fully charged lead-acid battery is subjected to constant current discharge for 30 minutes at 0.2CA, left for 15 minutes, and then the potential of the negative electrode is adjusted to Pb | PbSO4The charging current flowing during 20 minutes charging was measured with the electrode at-300 mV, and the dissolution rate of lead sulfate was measured by the nonlinear least squares method using equations 1 to 3,
the Pb | PbSO4The electrode was immersed in sulfuric acid having a specific gravity of 1.30 at 25 c,
[ mathematical formula 1]
Figure FDA0003062226830000031
[ mathematical formula 2]
Figure FDA0003062226830000032
Time of flight
Figure FDA0003062226830000033
Figure FDA0003062226830000034
Time of flight
Figure FDA0003062226830000035
[ mathematical formula 3]
Figure FDA0003062226830000036
Wherein, the unit and meaning of the parameter of the mathematical formula 1 to the mathematical formula 3 are as follows:
l is expressed in μm, and represents the length of one side of lead sulfate,
N(l0) Indicates a length of one side of l0The amount of lead sulphate in the lead-containing composition,
n in total represents the amount of total lead sulfate,
P(l0) Indicates a length of one side of l0The probability distribution of the number of lead sulfates,
lm in μm, representing P (l)0) The size parameter of (a) is,
the unit of alpha is mum and represents P (l)0) The shape parameter of (a) is,
i has the unit a, represents the current,
z represents a valence number, and z represents a valence number,
the unit of F is Cmol-1And the number of electrons representing the Faraday constant,
k has the unit of mol s-1cm-2The expression "indicates the dissolution rate of lead sulfate,
l0the unit of (d) is μm, and represents the length of one side of lead sulfate having t of 0,
m has the unit gmol-1It represents the molecular weight of lead sulfate,
rho is given in gcm-3And represents the density of lead sulfate.
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