JPH0679493B2 - Lead-acid battery function recovery agent and lead-acid battery function recovery method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is intended to clean the electrode plate of a lead acid battery (battery) by adding it to the electrolytic solution of the lead acid battery and to rapidly improve the ability of the lead acid battery with deteriorated function. The present invention relates to a function recovery agent for a lead storage battery containing an organic germanium compound, which can be recovered and greatly extend the service life of the lead storage battery, and a function recovery method thereof.

[Problems to be Solved by Prior Art and Invention]

A lead-acid battery consists of both pole (cathode) and pole (anode) terminals, can convert electrical energy into chemical energy by electrolysis, and can store it. It is a device that takes out the electric current by utilizing the redox action by decomposition.

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 electric resistance, in the case of automobiles, it can be called the force to rotate the starter motor) is a problem. For example, in the case of a 12V lead-acid battery for automobiles, even if the voltage is 12V or higher, if the electromotive force is 10V or lower, the starter motor cannot be turned. In addition, 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 electrolyte in lead acid batteries, and its specific gravity is 1.20 in lead acid batteries for automobiles.
The ones from 0 to 1.300 are used. 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. Also, when the battery is charged, the specific gravity will be 1.260 when the charging is completed. Since the specific gravity of the electrolytic solution and the 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.

The electrodes consist of lead (Pb) in the pole and lead oxide (PbO ₂ ) in the pole, and current flows from pole to pole in the discharged state and from pole to pole in the charged state.

During discharge, the chemical action in lead-acid batteries is that the electrode becomes lead sulfate (PbSO ₄ ) and the electrode also 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 electrodes of the electrodes return to lead, the electrodes return 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 there are the following four major weak points and it cannot avoid deterioration.

i) Sulfation [Production of lead sulfate (PbSO ₄ ) white non-conductor] ii) Hydrogen adverse effect iii) Self-discharge IV) Temperature change and its effect First, the sulfation is that the electrode plate is exposed from the liquid surface due to the decrease of the electrolytic solution. This is a phenomenon in which both lead in the pole and lead oxide in the pole become lead sulfate when discharged. 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 more or less lead-acid batteries, and even if it is a lead-acid battery with 100% electromotive force, it loses its power significantly and the specific gravity of dilute sulfuric acid decreases. Once the lead sulfate is formed inside, it cannot be removed even if charging is continued or repeated.

Next, the greatest weakness of the lead-acid battery is the harmful effect of hydrogen of ii). When the lead storage battery is charged, hydrogen gas is generated from the electrode and oxygen gas is generated from the electrode due to electrolysis. When hydrogen gas adheres to the surface of the electrode 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 will occur easily.

In addition, the self-discharge of iii) is a phenomenon in which hydrogen is generated as in ii), and when it is attached to the electrode, a polarization phenomenon occurs, so that one half cell is made, and as a result, self-discharge gradually occurs.

In addition, iv) temperature changes and their effects are caused by external temperature conditions. Dilute sulfuric acid, which is the electrolyte of lead-acid battery, has a specific gravity of 1.260 at + 20 ° C as described above.
The specific gravity changes 0.007 for a temperature change of 1 ° C. Therefore, even with a lead-acid battery with 100% electromotive force at + 20 ℃, it is -10 ℃.
Then, the electromotive force drops to 70%, and in cold regions such as below -30 ° C, the electromotive force falls below 50%, and problems due to freezing tend to occur. The trouble due to the 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 frequently used and the inside of the bonnet exceeds 90 ° C.
The electrolytic solution is rapidly decreased, the electric density is scattered, and troubles easily occur.

As described above, the lead acid battery has four major weaknesses and is inevitably deteriorated.

Conventionally, the specific gravity of an electrolytic solution 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 the electrolytic solution. However, this decrease in specific gravity is in the state where it has reached the above-mentioned sulfation.Therefore, when diluted sulfuric acid is added, the capacity of the electrolytic solution is exceeded and the electrode plate is seriously damaged, and the precipitation short circuit of the electrode plate and the abnormal occurrence of hydrogen gas are the maximum. As a result, the life of the lead acid battery is greatly shortened.

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 organogermanium compound has a specific electronic effect, and is a compound having a strong oxygen supply ability, which is effective as a function recovery agent for a lead storage battery, and based on this finding A patent application has already been filed (JP-A-59-194367).

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.

[Means for solving problems]

That is, the present invention is The present invention provides a function recovery agent for a lead-acid battery containing bis-β-ethylcarboxylic acid germanium sesquioxide represented by and an alkali metal or alkaline earth metal hydroxide as active ingredients.

Further, the present invention secondly provides a function recovery method for a lead storage battery, which is characterized in that the function recovery agent for the first lead storage battery according to the first invention of the present invention is added to the electrolytic solution of the lead storage battery.

In the first aspect of the present invention, bis-β-ethylcarboxylic acid germanium cesoxide represented by the above formula [I] is used as the organic germanium compound. 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, an alkali metal (lithium, sodium, potassium, rubidium, cesium) or an alkaline earth metal (calcium, together with the above-mentioned bis-β-ethylcarboxylic acid germanium sesquioxide) is used.
Strontium, barium, and radium) hydroxides are used.

The first lead-acid battery function recovery agent of the present invention contains the above raw materials as an active ingredient, and is usually used in the form of an aqueous solution. In this case, bis-β-ethylcarboxylic acid germanium sesquioxide 0.2 to 0.05% by weight is used. ,Preferably
0.2 to 0.1% by weight, 0.02 to 0.002% by weight of alkali metal or alkaline earth metal hydroxide, preferably 0.01 to 0.0
It is blended in a proportion of 01% by weight.

Here, even if each is blended 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 of the first lead storage battery of the present invention as described above.

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

〔The invention's effect〕

According to the present invention, there is an action of completely returning the sulfation to the original state, and the electrode plate can be washed to restore the conductivity and protect the electrode plate. In particular, the organic germanium compound used as a semiconductor quickly cleans the electrode plate by the electronic effect to increase the potential difference, so that the lead-acid battery can be charged quickly without difficulty. In addition, it is possible to suppress the decrease in voltage due to the electronic characteristics, recover the decreased voltage, and increase the electric capacity (function recovery) of the lead storage battery.

Further, according to the present invention, since a large amount of oxygen is supplied to the electrolyte of the lead storage battery, it is combined with hydrogen generated in the lead storage battery to form water, which completely suppresses the harmful effects of hydrogen as described above and improves the function of the lead storage battery. Can be increased. Moreover, since the hydrogen can be removed in this way together with the removal of the sulfation, the electrode plate becomes very clean and the current flow becomes good. Further, this can prevent self-discharge.

In addition, due to the electronic characteristics, when charging, the polarization of both electrodes becomes small and the voltage required for charging can be small, and the charging time can be shortened. Even during discharge, the polarization of both electrodes is small, so that the discharge voltage increases and it is possible to withstand discharge for a long time.

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. Moreover, by always adding the lead-acid battery, it is possible to keep the lead-acid battery with good performance, and this is a great contribution to the improvement of the starting performance of the automobile.

〔Example〕

 The present invention will be described below with reference to examples.

Example 1 To each cell of a used storage battery (YUASA Pafecta MF, manufactured by Yuasa Battery Co., Ltd.), 60 ml of an aqueous solution containing 0.1% by weight of germanium sesquioxide bis-β-ethylcarboxylic acid and 0.01% by weight of lithium hydroxide was averaged. The mixture was added and charged using the charger shown below, and the charging characteristics were measured using the following measuring device. The charging characteristics are the relationship between charging voltage and charging time (Fig. 1) and the relationship between specific gravity and charging time (Fig. 2).
FIG. 3) and the relationship between charging current and charging time (FIG. 3).

Charger Kelly Moel KC-6 Rated voltage 100V Rated input capacity 30VA Rated output voltage 12V (No load 14.1V) Measuring device KAISE Digital Multitester Example 2 Headlights of used storage batteries added and charged as in Example 1 It turned on and discharged until it went out. After 1 hour, discharge the light until the lights are turned on again,
It was completely discharged by repeating the operation once.

In this state, charging was performed in the same manner as in Example 1 and the charging characteristics were measured. The results are shown in FIGS. 1 to 3 as in the first embodiment.

Example 3 The storage battery charged according to Example 2 was discharged in the same manner as in Example 2, and then charged in the same manner as in Example 1. The results of measuring the charging characteristics are shown in FIGS. 1 to 3 as in Example 1.

Comparative Example 1 The charging characteristics were measured in the same manner as in Example 1 except that the aqueous solution containing bis-β-ethylcarboxylic acid germanium sesquioxide and lithium hydroxide was not added. The results are shown in FIGS.
This is shown as Comparative Example 1 (no addition) in the figure.

It is understood that by adding the function recovery agent of the present invention, the charging voltage and the specific gravity are increased, and the charging can be accepted promptly, the function of the lead storage battery can be recovered, and the service life can be extended.

Example 4 An actual vehicle test was conducted for one month using nine actual vehicles. That is, an aqueous solution containing 0.1% by weight of bis-β-ethylcarboxylic acid germanium sesquioxide and 0.01% by weight of lithium hydroxide before the operation for one month.
Two ml of the battery-enhancing liquid containing ml was injected into each cell of the lead acid battery (battery), and the change in the battery voltage was examined.

After one month, the following results were obtained.

6 units with increased voltage 2 units with unchanged voltage 2 units with reduced voltage 1 unit From this actual vehicle test, the following can be found. That is, in general, a lead storage battery has a voltage drop due to use and needs to be charged, but the addition of the function recovery agent (battery enhancer) of the present invention increases the voltage and increases the electric capacity, that is, The effects of increasing the function of the battery and extending the life of the battery are produced.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between charging voltage and charging time in Examples and Comparative Examples of the present invention, FIG. 2 is a graph showing the relationship between specific gravity and charging time, and FIG. 3 is charging current and charging. It is a graph which shows the relationship with time.

Claims (2)

[Claims] 1. A formula A function recovery agent for a lead-acid battery containing bis-β-ethylcarboxylic acid germanium sesquioxide represented by and an alkali metal or alkaline earth metal hydroxide as an active ingredient. 2. An electrolytic solution for a lead storage battery, comprising: Functional recovery of a lead-acid battery characterized by adding a function recovery agent for a lead-acid battery containing bis-β-ethylcarboxylic acid germanium sesquioxide represented by and an alkali metal or alkaline earth metal hydroxide as an active ingredient Method.