JPH0883621A - Function recovery liquid and function recovery method for lead-acid battery - Google Patents

Abstract

PURPOSE: To quickly recover the capability of a lead-acid battery having a function reduction and prolong the operating life by containing a surface active agent in an electrolyte, and using a perfluoroalkyl ethylene oxide addition product as the surface active agent. CONSTITUTION: A surface active agent is contained in the electrolyte of a lead- acid battery having a function reduction, and the boundary tension between the electrolyte and an electrode plate is reduced to 10-40-dyn/cm in particular by the infiltrating action of the surface active agent. When the surface active agent is used to reduce the boundary tension of the electrolyte, hydrogen bubbles are hardly stuck to the surface of an electrode, stuck bubbles are easily separated, the polarization by the hydrogen on the electrode is reduced, and a hydrogen trouble is reduced. When a perfluoroalkyl ethylene oxide addition product is used as the surface active agent, the capability of the lead-acid battery having a function reduction is quickly recovered, and the operating life can be sharply prolonged.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a lead-acid battery functional recovery liquid for rapidly recovering the function of a lead-acid battery whose function has deteriorated and greatly extending the service life of the lead-acid battery, and a function recovery of a lead-acid battery whose function has deteriorated. It is about the method. More specifically, by adding it to the electrolyte of a lead acid battery, it prevents sulfation and hydrogen damage of the lead acid battery, recovers the capacity of the lead acid battery that has deteriorated rapidly, and significantly extends the service life of the lead acid battery. The present invention relates to a function recovery liquid and a function recovery method for a lead storage battery that can be used.

[0002]

2. Description of the Related Art A storage battery is usually composed of a cathode, an anode and an electrolytic solution, and uses an oxidation-reduction reaction by electrolysis to convert electric energy into chemical energy and store it.
An electric current is produced from this chemical energy. For example, when a lead-acid battery is charged, the cathode becomes lead, the anode becomes lead oxide,
The electrolyte becomes dilute sulfuric acid, and when discharged, the lead oxide at the cathode becomes lead sulfate (PbSO ₄ ), and the lead oxide at the anode also becomes lead sulfate, and the sulfuric acid in the electrolyte is electrolyzed into water. Along with this chemical change, current flows from the anode to the cathode in the discharged state, and from the cathode to the anode in the charged state. Therefore, in principle, lead acid batteries should be used indefinitely. But,
With such a redox reaction and the flow of electricity, undesired side reactions and products are generated, which deteriorates the function of the lead storage battery. For example, lead oxide of the cathode and anode with discharge causes sulfation to form non-conducting crystals of white spots made of lead sulfate, and this electrode plate part can no longer store chemical energy due to charging, resulting in electromotive force of lead acid battery. Is reduced. In addition, when the lead storage battery is charged, hydrogen generated at the cathode becomes bubbles and adheres to the anode to cause a polarization phenomenon and become an insulating state, resulting in hydrogen failure. This hydrogen damage hinders the charging of the lead storage battery, and particularly when the battery is overcharged, hydrogen bubbles completely adhere to the surface of the electrode plate and no current flows. Furthermore, the hydrogen generated by self-discharge becomes bubbles and adheres to the anode to cause a polarization phenomenon, and the half-cell formed there promotes further discharge.

Therefore, if it is possible to prevent such electrochemical damage due to hydrogen damage, sulfation and self-discharge, the capacity of the lead storage battery is restored,
It is possible to extend the service life of lead acid batteries. Conventionally, as a function recovery method and a function recovery liquid of a lead storage battery,
JP-A-51-55932 and JP-A-59-19
Japanese Patent No. 4367 discloses bis-β-ethylcarboxylic acid silicon sesquioxide (SiCH ₂ · CH ₂ ·
COOH) ₂ O ₃ , germanium bis-β-ethylcarboxylate
Some have used organic semiconductors such as sesquioxide (GeCH ₂ , CH ₂ , COOH) ₂ O ₃ . And in the publication,
It is described that these organic semiconductors promote the redox action in the electrode, and at the same time, the action of the semiconductor reduces the polarization, thereby shortening the charging time and extending the discharging time. However, such a lead storage battery function recovery method and a function recovery liquid cannot overcome hydrogen damage due to hydrogen bubbles generated at the time of overcharging, and further, the lead storage battery function is effectively, and It was desired to recover quickly.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a function recovery liquid for a lead storage battery, which rapidly recovers the performance of a lead storage battery having a deteriorated function and greatly extends the service life of the lead storage battery, and a lead storage battery having a deteriorated function. The purpose is to provide a function recovery method.

[0005]

As a result of research for solving the above-mentioned problems, the present inventors have found that the interfacial action of a surfactant reduces the interfacial tension between the electrolyte and the electrode plate,
It was found that the function of the lead storage battery is effectively and promptly restored by setting the interfacial tension to 10 to 40 dyn / cm. Therefore, the present invention provides a function recovery liquid for a lead storage battery, which is characterized by containing a surfactant, and a small interfacial tension between the electrolytic solution and the electrode plate due to the osmotic action of the surfactant, particularly 10 to 40 dyn / cm. A method for recovering the function of a lead storage battery is provided. Furthermore, in the present invention, the interfacial tension of the lead acid storage function recovery liquid and the electrolytic solution is 10 to 10.
Provided is a lead acid battery having a content of 40 dyn / cm.

In the present invention, the surfactant is used to reduce the interfacial tension of the electrolytic solution so that the electrodes and the separator of the storage battery are well adapted to the electrolytic solution, that is, sufficiently wetted. If this wetting is not sufficient, the ions in the electrolyte cannot contact the electrodes and separators, increasing the electrical resistance of the separators and electrodes, and narrowing the effective reaction area of the electrodes, resulting in battery discharge voltage. Lower energy efficiency. On the other hand, if a surfactant is added to the electrolytic solution to lower the interfacial tension of the electrolytic solution, the electrolytic solution will enter between the crystals of lead sulfate, which has poor wettability, and the current density during charging will decrease, and overdischarge will also occur. Charge acceptability after leaving is improved. Furthermore, if a surfactant is used to reduce the interfacial tension of the electrolyte, hydrogen bubbles will not easily adhere to the electrode surface, and even if they adhere, they will easily separate, so there will be less polarization due to hydrogen on the electrode. And so-called hydrogen damage is greatly reduced.

The surfactant used in the present invention can be used without particular limitation as long as it is not decomposed by an electrolytic solution and can exert a surfactant effect. For example, specific examples of the surfactant of the present invention include lignin sulfonate, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, Alkyl phosphates, fatty acid salts such as polyoxyethylene alkyl or alkylallyl sulfate ester salts, anionic surfactants such as naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxy Ethylene derivative, polyoxyethylene
Specialty polycarboxylic acid type polymer surfactants such as oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine , Nonionic surfactants such as alkylbetaine, and also cationic surfactants and amphoteric surfactants, and these surfactants can be used alone or in combination.

Of these surfactants, preferred are lignin sulfonates, perfluoroalkylcarboxylic acid salts, and perfluoroalkylethylene oxide adducts, and particularly preferred are perfluoroalkylethylene oxide adducts. is there.

In the lead-acid battery function recovery liquid of the present invention, organic germanium can be used in combination with the above-mentioned surfactant. The reason for combining this organic germanium is that the permeation of the surfactant and the semiconductor-like action of the organic germanium cause a current to flow little by little to the inactive part (the electrode part covered with the plate-shaped lead sulfate). As a result, the starting power of the lead storage battery can be restored to near the original state. Among these organic germanium, preferable ones are bis-β-ethylcarboxylic acid silicon sesquioxide (SiCH ₂ · CH ₂ · COOH) ₂ O ₃ , which is disclosed in JP-A-59-194367.
And bis-β-ethylcarboxylic acid germanium sesquioxide (GeCH ₂ · CH ₂ · COOH) ₂ O ₃ . Further, as the surface active agent, an antifoaming agent or a surface active agent having a low surface tension and having an antifoaming property can be used if necessary. In particular, in order to prevent the generation of bubbles of hydrogen and oxygen in the electrode and to eliminate the bubbles once generated, it is preferable to use a surfactant having a defoaming property in the function recovery liquid. Generally, the amount of the surfactant or defoaming agent to be added to 100 parts by weight of organic germanium varies greatly depending on the type, and for example, in the case of perfluoroalkylethylene oxide adduct, 300 to 100 parts by weight,
It is preferably 200 to 250 parts by weight.

The composition of the functional recovery liquid for lead-acid battery of the present invention is
You can freely change it as needed. Further, when the function recovery liquid for lead acid battery of the present invention is added to the electrolytic solution of the lead acid battery, the amount of the surfactant is such that the interfacial tension of the electrolytic solution is 15 to 4
It is suitable to set it to 0 dyn / cm, preferably 20 to 30 dyn / cm. When the interfacial tension is lower than 15 dyn / cm, the electrolytic solution overflows from the lead storage battery when the lead storage battery is rapidly charged, and the water level of the electrolyte drops below the standard at the end of charging (it is necessary to replenish the electrolyte newly). On the other hand, when the interfacial tension is higher than 40 dyn / cm, the defoaming property is deteriorated and there is no difference from general commercial products, which is not preferable.
Generally, the amount of the surfactant of the present invention varies greatly depending on the kind of the surfactant, and particularly when a perfluoroalkylethylene oxide adduct is used, the concentration thereof is 0.0001 to 0.1% by weight based on the weight of the electrolytic solution. %, Especially 0.00
It is preferably from 03 to 0.01% by weight.

[0011]

EFFECTS OF THE INVENTION With the function recovery liquid for lead acid battery of the present invention,
It is possible to rapidly recover the capacity of a lead-acid battery whose function has deteriorated, and to prolong the service life of the lead-acid battery significantly. further,
The lead storage battery containing the function recovery liquid for lead storage batteries of the present invention is less likely to have a decline in function and has a long service life. In particular, the lead-acid battery of the present invention containing the surfactant of perfluoroalkylethylene oxide adduct has significantly improved the charge acceptability of the lead-acid battery after being left over-discharged. Therefore, the lead-acid battery of the present invention can be completely charged in the same charging time as immediately after discharging, even if it is left overdischarged. Next, the function recovery method and function recovery solution for a lead storage battery of the present invention will be described in detail with reference to examples.

[0012]

【Example】

[Examples 1 and 2, Comparative Examples 1 to 7] First, the effect of functional recovery of the lead storage battery according to the present invention will be described. (Lead storage battery) In this embodiment, the following 12V lead storage battery was used. Used A: Furukawa Battery LOT. 22FILV Used B: HITACHI LOT. XD825CR Used C: HITACHI LOT. XA110N Next, as shown in Table 1, the experiments of Examples 1 and 2 and Comparative Examples 1 to 7 were performed using a lead storage battery and an additive. As the additive, an organic germanium compound, an organic metal compound, an inorganic compound, or a surfactant was used. In particular, a perfluoroalkylethylene oxide adduct was used as this surfactant. These additives were added as follows. The electrolytic solution was taken out from each lead-acid battery cell by 433.3 ml / cell (2600 ml / 6 cells = 433.3 ml / cell), and 10 ml of the required additive was added to the taken out electrolytic solution.
/ Cell (10 ml / cell × 6 cells = 60 ml) was added. After the additive is completely dissolved, return the electrolyte to each original cell,
It was left for about 3 hours to homogenize. The reason why the additive was dissolved in the electrolytic solution instead of distilled water and returned to the original cell was
This is to eliminate the effect of diluting the electrolytic solution with distilled water.

(Charging and Discharging Conditions of Lead Acid Battery) The lead acid battery thus prepared was charged and discharged under the following conditions.
RU of Stanley Electric Co., Ltd. as a battery charger
As SH-3, Digital Multilester CD-710C manufactured by Sanwa Electric Instruments Co., Ltd. was used as a voltage / current measuring device. A charge of 12 V was applied to each of the lead acid batteries described above and charged for 16 hours. Next, a load was applied with one 12V / 100W light bulb, and the lead storage battery was discharged until the voltage reached 10.5V (cell motor rotation limit), and the discharge time was measured. In order to prevent the temperature change of the lead storage battery electrolyte during discharge, the lead storage battery was immersed in a constant temperature water tank (Automatic electronic constant temperature water tank of Ikemoto Rika Kogyo) and kept at 20 ° C. at room temperature.

(Criteria for Judgment) The lead storage batteries prepared in Comparative Examples and Examples from which the voltage of the lead storage battery was changed from 12.5 V to 10.5 V were discharged, and the time was measured. With the discharge time of the lead-acid battery without addition of the additive as 100, the ratio of the discharge time of each comparative example and the example was obtained, and the performance of each lead-acid battery was compared. The obtained results are shown in Table 1. The relationship between the comparatively evaluated performance evaluation and the measurement result of the interfacial tension is as follows. As is clear from the description in Table 1, in Examples 1 and 2, the addition of the surfactant resulted in an interfacial tension of 27,
It is 28 dyne / cm, which is clearly low, and the discharge time is obviously long. Therefore, it is clear that the effect of the present invention is remarkable. On the other hand, Comparative Example 2 using a conventional lead storage battery deterioration prevention method and deterioration prevention liquid
In ~ 6, there is almost no difference in the time required for discharging from the lead storage batteries obtained in Comparative Examples 1 and 3 which are symmetrical to each other,
On the contrary, even a negative effect was seen.

[0015]

[Table 1] Table 1 Comparative Example Example 1 2 3 4 5 6 7 1 2 Amount of additive 1. Organic semiconductor (mg) ethyl carboxy-180 360-360 360--90 germanium sesquioxide (Ge CH ₂ COOH) ₂ O ₃ 2.Organometallic compound (mg) Nasem / magnesium ¹⁾ 10 Nasem / aluminum ²⁾ 13 3.Inorganic compound (mg) CoSO ₄ / 7H ₂ O (oxidizer) 11 MgSO ₄ / 7H ₂ O (oxidizer) 10 Al ₂ (SO ₄ ) ₃・ 14-18H ₂ O (reducing agent) 25 4. Surfactant (mg) Perfluoroalkyl--------260 Ethylene oxide adduct Lignin sulfone------ -260- Acid soda Lead acid battery type AAABBBCCC Discharge time (min) 219 214 212 83 82 73 170 186 188 Discharge time ratio (%) 100 98 97 100 99 88 100 109 111 Performance evaluation-None-None-Effect Effect Effect Large Large Large Interfacial tension (dyn / cm) 72 77 76 72 77 75 72 28 27

[0016]

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[Example 3] The effect of a surfactant when the function recovery liquid of the present invention was continuously used was examined. The same 12V used lead-acid battery as in Example 1 was used, and a perfluoroalkylethylene oxide adduct was used as a surfactant. The concentration of the surfactant is as shown in Table 2,
Six lead acid batteries were used. First, charging and discharging of a lead storage battery were repeated without adding an additive, and the state of foaming around the cell liquid surface was observed. Then, while repeating charging and discharging of the lead storage battery, a surfactant was added at regular intervals and the state of foaming around the cell liquid surface was observed. As a criterion for evaluation, if no bubbles were present, the charging performance was insufficient, and if bubbles were too large to overflow the electrolytic solution, it was determined that the surfactant was excessive. As a result, when the concentration of the surfactant was less than 0.0001% by weight, no bubbles were formed around the cell liquid surface, which was insufficient as charging performance, and conversely, it was less than 0.
When it exceeded 1% by weight, bubbles were too much and the electrolyte overflowed. On the other hand, it was confirmed that when the concentration of the surfactant was 0.0003 to 0.01% by weight, the battery was charged in the best condition. It should be noted that if charging and discharging the lead-acid battery is repeated without adding a surfactant, the charging performance will decrease, and if a surfactant is added at a fixed interval later, the charging performance will be restored again. I was able to confirm.

As is clear from the above description, the following effects are obtained by using the function recovery method and the function recovery solution for a lead storage battery according to the present invention. First, the electromotive force of the deteriorated lead storage battery was returned to the original state. Second, the chemical reaction in the lead acid battery was activated, and the aging of the battery was suppressed.
Third, as compared with the conventional function recovering agent, when the function recovering agent of the present invention is used, the interfacial tension becomes smaller, so sulfation and hydrogen damage are suppressed, and self-discharge is reduced.
Fourthly, the startability on cold days was improved, and fifthly, the charging time was shortened and the charging power was increased.

Claims (11)

[Claims] 1. A function recovery liquid for a lead storage battery, which contains a surfactant. 2. The lead-acid battery function recovery liquid according to claim 1, wherein the surfactant is a fluorine-based surfactant. 3. The function recovery liquid for a lead storage battery according to claim 2, wherein the surfactant is a perfluoroalkylethylene oxide adduct. 4. The lead-battery function recovery liquid according to claim 1, further comprising organic germanium. 5. A method for recovering the function of a lead storage battery, which comprises reducing the interfacial tension between the electrolytic solution and the electrode plate by the permeation action of a surfactant. 6. A method for recovering the function of a lead storage battery, which comprises adding the function recovery solution for a lead storage battery according to claim 1 to an electrolytic solution of the lead storage battery. 7. A function recovery method for a lead storage battery, comprising adding the lead storage battery function recovery solution according to claim 3 to an electrolyte solution for a lead storage battery, wherein the weight of the electrolyte solution is used as a reference. Perfluoroalkyl ethylene oxide adduct is 0.
A method for recovering the function of a lead storage battery, which comprises adding a function recovery solution for a lead storage battery to a concentration of 0001 to 0.1% by weight. 8. The interfacial tension of the electrolyte is 10-40 dyn / cm.
The method for recovering the function of a lead storage battery according to any one of claims 5 to 7, wherein: 9. The interfacial tension of the electrolyte is 10 to 40 dyn / cm.
Lead acid battery characterized by being. 10. A lead storage battery, wherein the electrolytic solution contains the function recovery liquid for lead storage battery according to any one of claims 1 to 4. 11. The lead acid battery according to claim 10, wherein the electrolytic solution contains 0.0001 to 0.1% by weight of a perfluoroalkylethylene oxide adduct.