JPH05225999A - Function restoration agent for lead-acid battery and function restoration method for lead-acid battery - Google Patents

Abstract

PURPOSE:To greatly increase the service life of a leadacid battery by cleaning a pole plate of the lead-acid battery and causing rapid restoration of the function of the same. CONSTITUTION:The above identified function restoration agent for lead-acid battery is one which contains as an effective component one of bis-beta-ethyl carboxylic acid germanium sesquioxide, cadmium sulfuric acid, and hydroxide of alkali metal or alkali earth metal. the use of this agent enables suppressing a drop of the voltage and restoring the lowered voltage, thereby causing an effective increase in electric capacity (function restoration) of the lead-acid battery.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a lead storage battery (battery) which is added to an electrolytic solution to clean the electrode plate of the lead storage battery and to rapidly restore the function of the lead storage battery whose function has deteriorated. The present invention relates to a function recovery agent for a lead-acid battery containing organic germanium and cadmium sulfate, which can significantly extend the service life of, and a method for recovering the function.

[0002]

2. Description of the Related Art A lead-acid battery is composed of a negative electrode (cathode) and a positive electrode (anode), and can be stored by converting electric energy into chemical energy by electrolysis. This is a device for extracting electric current by utilizing so-called redox action by electrolysis, which converts chemical energy into electric energy again as needed.

In the case of lead-acid batteries for automobiles, electric current is constantly supplied from a generator (dynamo) while traveling and regulated by a regulator. However, in the case of lead-acid batteries for automobiles, electromotive force (voltage measured through electrical resistance,
In the case of an automobile, it can be said to be the force that rotates the starter motor. ) Becomes a problem. For example, in the case of a 12V lead-acid battery for automobiles, the electromotive force is 1 even if the voltage is 12V or higher.
When it becomes 0V or less, the starter motor cannot be turned.
Further, since the electric current of about 3 times the rated current actually flows in the rotation of the cell motor, the voltage of the lead storage battery is rapidly consumed when the cell motor is continuously rotated several times. Therefore, in the above cases, charging is required.

By the way, dilute sulfuric acid (H ₂ SO ₄ ) is used as the electrolytic solution of the lead storage battery, and its specific gravity is 1.2000 to 1.300 in the lead storage battery for automobiles. .. The best condition for conducting electricity is 1,260 at + 20 ° C., the specific gravity decreases as the discharge progresses, and the average specific gravity when fully discharged is 1.050.
Becomes When the battery is charged, the specific gravity becomes 1.260 when the charging is completed. Since the specific gravity of the electrolytic solution and the amount of electricity (charge amount) are thus directly proportional to each other, the state of charge can be known by measuring the specific gravity of the electrolytic solution. Generally, the specific gravity of the electrolytic solution is preferably in the range of 1.180 to 1.260, and when it is less than 1.150, charging is required.

In the electrode, the negative electrode is made of lead (Pb) and the positive electrode is made of lead oxide (PbO ₂ ). In the discharge state, the current is changed from the positive electrode to the negative electrode.
The current flows from the negative pole to the positive pole in the charged state. In the chemistry of lead acid batteries, during discharge, the negative electrode is lead sulfate (PbSO4).
_{In 4} ), and also the + electrode becomes lead sulfate, and the electrolytic solution changes from dilute sulfuric acid and water to water by electrolysis. On the other hand, at the time of charging, the negative electrode of the electrode returns to lead, the positive electrode returns to lead oxide, and the electrolytic solution returns to its original state like diluted sulfuric acid and water.

Therefore, according to the principle of this charging / discharging action,
It should be possible to use it for a considerably long period of time by appropriately charging it, but it has the following four major weaknesses and is inevitable for deterioration. (I) Sulfation [Production of lead sulfate (PbSO ₄ ) white insulator] (ii) Hydrogen poisoning (iii) Self-discharge (iv) Temperature change and its effect

First, sulfation is a phenomenon in which both the negative electrode lead oxide and the positive electrode lead oxide become lead sulfate when the electrode plate is exposed or discharged from the liquid surface due to the decrease of the electrolytic solution.
When the lead acid battery is completely discharged, it causes sulfation, and since this lead sulfate is a non-conductor, it stops conducting electricity and cannot accept any charge. This sulfation is a phenomenon that occurs in any or all of the lead-acid batteries, and the lead-acid battery having an original electromotive force of 100% loses its power remarkably, and the specific gravity of dilute sulfuric acid decreases. The lead sulfate once formed inside cannot be removed even if charging is continued or repeated.

Next, the biggest weakness of the lead-acid battery is (i
This is the adverse effect of hydrogen on i). When the lead storage battery is charged, electrolysis produces hydrogen from the negative electrode and oxygen gas from the positive electrode. When hydrogen gas adheres to the + electrode surface in the form of bubbles, the surface causes a polarization phenomenon and becomes an insulating state, and when completely adhered, no current flows. Moreover, if there is a place where current does not easily flow even with one pole, heat will be generated only in that pole and the amount of the electrolyte solution will particularly decrease, so that sulfation is likely to occur.

The self-discharge of (iii) is (i)
When hydrogen is generated and attached to the positive electrode as in the case of i), a polarization phenomenon occurs, so that one half-cell is created, and as a result, self-discharge is gradually occurring.

Further, the temperature change (iv) and its influence occur due to the external temperature condition. The specific gravity of dilute sulfuric acid, which is the electrolytic solution of the lead storage battery, is set to 1.260 at + 20 ° C. as described above, and the specific gravity changes 0.007 with respect to the temperature change of 1 ° C. Therefore, 100% at + 20 ° C
Even with a lead storage battery having an electromotive force of 10, the electromotive force drops to 70% at -10 ° C, and the electromotive force falls below 50% at -30 ° C or less in a cold region, and troubles due to freezing easily occur. This trouble due to freezing is more likely to occur when the discharge progresses and the electrolytic solution is close to water.
On the other hand, when the temperature is high, the cooler is often used and the inside of the bonnet exceeds 90 ° C., so that the electrolytic solution sharply decreases, the electric density becomes diffused, and troubles easily occur.

As described above, the lead storage battery has four major weaknesses and is inevitably deteriorated. Conventionally, specific gravity has been measured, and diluted sulfuric acid has been added to a lead storage battery having a reduced specific gravity to increase the specific gravity of an electrolytic solution. However, this decrease in specific gravity is in the above-mentioned sulfation state, and therefore the addition of dilute sulfuric acid causes the electrolyte capacity to be exceeded, which seriously damages the electrode plate, which causes precipitation short circuit of the electrode plate and abnormal occurrence of hydrogen gas. This causes the lead-acid battery life to be greatly shortened.

[0012] Therefore, the present inventors have made extensive studies in order to solve the above conventional problems. As a result, it was found that a specific organic germanium compound has a specific electronic effect, and is a compound having a strong oxygen supply ability, and is effective as a function recovery agent for a lead storage battery, and based on this finding A patent application has already been filed (Japanese Patent Laid-Open No. 59-1943).
67 and 63-19711). The present invention relates to the improved technology of the above invention, and an object thereof is to provide a function recovery agent and a method for recovering the function thereof, which can further extend the service life of a lead acid battery.

[0013]

That is, the first aspect of the present invention is
In addition, (a) Formula (I)

[Chemical 3] To provide a functional recovery agent for a lead-acid battery containing bis-β-ethylcarboxylic acid germanium sesquioxide represented by the formula (b), cadmium sulfate (b) and (c) an alkali metal or alkaline earth metal hydroxide as an active ingredient. Is. Furthermore, the present invention secondly provides an electrolytic solution for a lead storage battery,
It is intended to provide a function recovery method for a lead storage battery, which is characterized in that the function recovery agent for a first lead storage battery according to the present invention is added.

In the first aspect of the present invention, bis-β-ethylcarboxylic acid germanium sesquioxide represented by the above formula (I) is used as the organic germanium compound as the component (a). Even if another organic germanium compound is used, the effect of the present invention cannot be obtained.

Further, in the first aspect of the present invention, (b) cadmium sulfate is used together with (a) bis-β-ethylcarboxylic acid germanium sesquioxide. The cadmium sulfate is usually represented by CdSO ₄ .8 / 3H ₂ O, but other hydrates can be used.

Further, in the first aspect of the present invention, as the component (c), an alkali metal (lithium, sodium, potassium, rubidium, cesium) or an alkaline earth metal (calcium, strontium, barium, radium) is used.
Hydroxide is used.

The first lead-acid battery function recovery agent of the present invention is
It contains the above raw materials as an active ingredient and is usually used in the form of an aqueous solution. In this case, the blending ratio of each component is not particularly limited, but usually (a) bis-β-ethylcarboxylic acid germanium sesquioxide is 0.2 to 0.
01% by weight, preferably 0.1 to 0.02% by weight, (b) cadmium sulfate is 0.1 to 0.005% by weight, preferably 0.05 to 0.01% by weight,
(C) The alkali metal or alkaline earth metal hydroxide is 0.02-0.002% by weight, preferably 0.01-.
The proportion is 0.001% by weight. Here, even if each is mixed in excess of the upper limit, it is not possible to obtain an effect commensurate with the blended amount. On the other hand, if the blending amount is less than the lower limit,
The desired effect cannot be achieved. If necessary, other additives may be appropriately added to the function recovery agent for the first lead storage battery of the present invention as described above.

Next, in the second aspect of the present invention, the above-mentioned first function recovery agent of the present invention is added to the electrolytic solution of the lead storage battery. The amount of addition is 60 ml of aqueous solution, 24 for a 12 V battery.
120 ml is suitable for V battery.

[0019]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Used storage battery (YUASA
Pafecta MF, Yuasa Battery Co., Ltd., battery capacity 3
An aqueous solution containing 0.08 wt% of bis-β-ethylcarboxylic acid germanium sesquioxide, 0.03 wt% of cadmium sulfate and 0.01 wt% of lithium hydroxide in each cell of a 6 AH automobile battery) The test was performed by adding 60 ml of "G") to the average and repeating charging, pausing, discharging, pausing and charging using the test apparatus shown in FIG. Test equipment Since there is no ready-made test equipment that satisfies the purpose, the storage battery used for the test is specially designed to comply with the JIS standard, and the actual resistance in the manufacturing process and the input / output of the circuit Great care was taken to minimize the influence of resistance on the test results. FIG. 1 is a block system diagram of the test apparatus. As shown in the figure, a regulator 1 (source for charging / discharging a storage battery to be tested based on JIS standard) and a comparator 2 (reference voltage for determining discharge end voltage) Source), controller 3
It consists of five components: a controller that determines the charging / discharging / pause time and its cycle, a recorder 4 (continuous recording of data), and a load resistor 5 (load for setting a specified discharge current). Test method After charging for 2 hours and resting for 1 hour in the circuit of FIG. 1,
Discharge starts and the terminal voltage of the battery is 10.5V (Volt)
When the voltage has dropped to 0, the circuit is automatically disconnected, the circuit is paused for 1 hour and charging is restarted, and the voltage and current during this period are automatically recorded in the recorder 4. Each cycle was basically 10 times. Analysis Method Generally, the performance of a storage battery is determined by the amount of energy it has and the power conversion efficiency, that is, the ratio of input energy to output energy. In addition, it is necessary to consider the ambient temperature and the resistance to rapid charge and rapid discharge, but this time we mainly conducted tests in response to the former. As shown in FIG. 2, the charging characteristic of the battery according to the JIS standard rapidly shifts to the drooping characteristic when a constant current continues for a certain time and the completion of charging approaches. The constant current period and the drooping characteristic are unique to each battery, and these can be used as factors for estimating the amount of charging energy. As a result of the experiment, it was found that this drooping characteristic can regress to an exponential curve having a certain constant. Here, the Y-axis, that is, the I-constant straight line of the current axis is P at the intersection with the regression curve.
The tangent line passing through P is the X axis, that is, the point of intersection with the time axis is X, and the area surrounded by the origin O and IPX is considered as charging energy, and a straight line of (1/2) I-constant intersects with the tangent line. The line segment TC is a representative value of charging energy. Since the discharge end voltage is set to a constant value, the line segment TD corresponding to the time from the start of discharge to the discharge end voltage is the representative value of the discharge energy. When the charge / discharge energy is specified as described above, the power conversion efficiency PC is represented by PC = TD / TC. It is conceivable that the PC will gradually become smaller as the battery ages due to repeated charging and discharging. Therefore, for the above-mentioned used battery, after repeating charging and discharging without "G", adding "G" and repeating charging and discharging again, the P
Changes in C, that is, changes in aging characteristics were compared using the method of linear regression. Batteries, especially used batteries, have very different solid differences due to differences in their history, so it is difficult to use a separate battery to compare "G" -containing and "G" -less (hereinafter simply "NG") with a small number of samples. Therefore, the same battery was tested.

The results of the test are shown in Tables 1 to 4, and the meaning of "Nation" used here is as follows. In the table, for example, "G-1" means "first time with G", and "NG-1" means "first time without G".
Is the meaning of. PC Power conversion efficiency TC Typical value of charging energy TD Typical value of discharging energy SD Standard deviation TCm Average value of charging energy TDm Average value of discharging energy TT Sum total XP Regression index Curve-I-constant straight line intersection XT Regression index The tangent of the curve XP intersects with the straight line of I = O Vmin Discharge end voltage A, B Constant of exponential equation DF Tangent slope YI Constant current value I = YI a, b Constant of linear regression equation XP, YP Coordinates XQ, YQ Coordinate

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

[0028]

[Table 8]

[0029]

[Table 9]

[0030]

[Table 10]

[0031]

[Table 11]

[0032]

[Table 12]

[0033]

[Table 13]

[0034]

[Table 14]

[0035]

[Table 15]

When TT, PCm, and SD are obtained based on the numerical values in Tables 1 to 4, Tables 5 to 8 are obtained.

[0037]

[Table 17]

[0038]

[Table 18]

[0039]

[Table 19]

[0040]

[Table 20]

The PCs in the case of NG and the case of G in "battery No. = S-6" are shown in Tables 9 and 10.

[0042]

[Table 21]

[0043]

[Table 22]

PCs based on Tables 9 and 10 are graphically displayed as aging lines in FIGS. 3 to 5.
As is clear from FIGS. 3 and 4, in NG, PC
Clearly decreases, but when G is added, it is found to pass in the increasing direction as shown in FIG. As shown in FIG.
A recurrence up to 2 times shows a downward trend, but Fig. 3
It is gentle compared to. FIG. 6 is a diagram in which the aging straight line in NG of PC and the aging straight line in the presence of G are continuous, and as is clear from this figure, it is well understood that the effect of adding G is large.

Table 11 shows the PCs in the case of NG and the case of G in "battery No. = S-7".

[0046]

[Table 23]

FIGS. 7 and 8 show the PC of Table 11 as an aging line.
o. = S−7 ”, as shown in FIG. 7, even in NG, the number of PCs tends to increase up to the 10th time. However, as shown in Table 12, this is divided into 5 times,
When this is displayed graphically as shown in FIGS. 9 and 10, it is found that both are decreasing.

[0048]

[Table 24]

On the other hand, in FIG. 8 when G is included, the increasing tendency seems to be slow, but this is divided into 5 times as shown in Table 13, and is divided and displayed as shown in FIGS. 11 and 12. It turns out that the effect of adding G is great.

[0050]

[Table 25]

Table 14 shows the 11th and subsequent PCs when the charge / discharge is repeated 14 times with G in "battery No. = S-7".

[0052]

[Table 26]

FIG. 13 shows this by connecting it to the aging straight line in the case of NG. As is apparent from FIG. 13, it is found that the aging straight line becomes slow when G is included. ..

[0054]

According to the present invention, as is clear from the analysis result, the aging of the battery becomes remarkably slow, and the life of the battery can be extended. This is considered to be due to the action of restoring sulfation to the original level, the action of washing the electrode plate to restore the conductivity, and the action of protecting the electrode plate. This is because the lead-acid battery accepts charging quickly and reasonably by rapidly cleaning the electrode plate and increasing the potential difference due to the electronic effect of the organic germanium compound used as a semiconductor. In addition, it is possible to suppress the decrease in voltage due to its electronic characteristics and recover the decreased voltage to increase the electric capacity of the lead storage battery [function recovery]. Further according to the invention,
Since a large amount of oxygen is supplied to the electrolytic solution of the lead storage battery, it is combined with hydrogen generated in the lead storage battery to form water, and the above-mentioned harmful effects of hydrogen can be completely suppressed to enhance the function of the lead storage battery. As described above, by adding the function recovery agent of the present invention to the electrolytic solution of a lead storage battery having a deteriorated function, the function can be promptly recovered. Further, by always adding it, it is possible to keep the lead storage battery with good performance at all times, which greatly contributes to the improvement of the starting performance of the automobile.

[Brief description of drawings]

FIG. 1 is a block system diagram of a test apparatus.

FIG. 2 is a graph diagram for explaining an analysis method.

FIG. 3 is a fluff diagram showing the power conversion efficiency of NG in Table 9 as an aging line.

FIG. 4 is a fluff diagram showing the power conversion efficiency with G in Table 9 as an aging line.

FIG. 5 is a graph showing the power conversion efficiency with G in Table 10 as direct aging.

FIG. 6 is a graph diagram in which an aging straight line for NG and an aging straight line for G are continuously displayed.

FIG. 7 is a graph showing the power conversion efficiency of NG in Table 11 as an aging line.

FIG. 8 is a graph showing the power conversion efficiency with G in Table 11 as an aging line.

FIG. 9 is a graph showing the power conversion efficiency of the first five times of Table 12 as an aging straight line.

FIG. 10 is a graph showing the power conversion efficiency of the last five times of Table 12 as an aging line.

FIG. 11 is a graph showing the power conversion efficiency of the first five times in Table 13 as an aging straight line.

FIG. 12 is a graph showing the power conversion efficiency of the last five times of Table 13 as an aging line.

FIG. 13 is a graph showing the power conversion efficiency of Table 14 as an aging line.

[Table 16]

Claims (4)

[Claims] 1. (a) Formula (I): A function recovery agent for a lead-acid battery containing bis-β-ethylcarboxylic acid germanium sesquioxide represented by the formula (b), cadmium sulfate (b) and (c) a hydroxide of an alkali metal or an alkaline earth metal as active ingredients. 2. The content of bis-β-ethylcarboxylic acid germanium sesquioxide is 0.2 to 0.01% by weight.
And the content of cadmium sulfate is 0.1 to 0.005.
The function recovery agent according to claim 1, wherein the function recovery agent is in weight%. 3. An electrolytic solution of a lead storage battery, wherein (a) formula (I): Bis-β-ethylcarboxylic acid germanium sesquioxide represented by the formula (b), (b) cadmium sulfate and (c) and a functional recovery agent for a lead-acid battery containing a hydroxide of an alkali metal or an alkaline earth metal as an active ingredient are added. A method for recovering the function of a lead storage battery, which is characterized by the above. 4. The amount of the function recovery agent added to the electrolytic solution of the lead acid battery is 0.2 to 0.01% by weight of germanium sesquioxide bis-β-ethylcarboxylic acid, and the amount of cadmium sulfate 0.1 to 0. The function recovery method according to claim 3, wherein the content is 005% by weight.