JP2851729B2 - Large-capacity colloid storage battery, colloid electrolyte used therefor, and method for producing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a secondary battery, a colloid electrolyte used in the secondary battery, and a method for producing the same.

[0002]

2. Description of the Related Art Lead-sulfuric acid batteries, which are currently one of the main types of batteries in the world, have a wide variety of applications, low cost,
And various advantages such as well-developed manufacturing methods. However, this presents drawbacks such as acid leaks and spills, the release of large amounts of acid mist during charging and discharging, high self-discharge rates, short operating life, the need for many maintenance tasks, etc., and often sulfuric acid regulation and Since addition is necessary, it is inconvenient for transportation, practical use and maintenance. In addition, the release of a large amount of acidic mist causes environmental pollution. Acid mist released from the storage battery during factory charging has an unpleasant and irritating odor, making breathing difficult. Many harmful substances, including sulfur dioxide, hydrogen sulfide, sulfuric acid mist, etc., are present in this acidic mist. Sulfur dioxide has been reported to have irritant effects on the human respiratory tract. When the concentration of sulfur dioxide reaches 10-15 ppm, the motility of the airway peristaltic hair is impaired and the mucous membrane is damaged, and when the concentration of sulfur dioxide reaches 20 ppm, its irritating effect is clearly increased with coughing cause. Furthermore, sulfur dioxide has a carcinogenesis promoting action, and a sulfur dioxide concentration of 10 mg / m ³ promotes carcinogenicity of carcinogenic benzo (a) pyrene. Sulfur dioxide also affects the growth and development of various organisms. Hydrogen sulfide has a bad smell and has toxic effects on humans. The stimulating effect of sulfuric acid mist is higher than that of sulfur dioxide 1
It is as high as 0-fold (China Encyclopedia, Environmental Sciences, December 68, Beijing, Shanghai, China Encyclopedia, p. 68, p. 258), and severely impairs human health. Since the sulfuric acid storage battery has an acid leak, the leaked acid strongly corrodes the storage battery itself and devices. Accidents that cause burns to the workers 'skin during the charging process often occur and impair the workers' health.

Many colloid electrolyte storage batteries have been studied since the first US patent was issued in 1921, including a method for producing a colloid electrolyte, and numerous patents or other publications have been published in this field. ing. China Patent No.
86102428 describes a silica gel storage battery, the filling material of which is a colloidal electrolyte consisting of coconut powder, sulfuric acid and sodium silicate. Its sulfuric acid (specific gravity
1.48-1.58) vs. sodium silicate (specific gravity 1.05-1.09)
The ratio of coconut shell powder is 0.5-1.5: 5-1.5: 0.004-
0.008, and preferably 1: 1: 0.06. The separator in this battery is made of glass fiber.

[0004] Chinese Patent 86209279U describes a silica gel electrolyte lead-sulfuric acid battery, wherein the gel electrolyte comprises sulfuric acid and a gelling agent for sulfuric acid. The gelling agent consists mainly of silicon dioxide, and glycerol is added as a stabilizer to form the silica sol. The gel electrolyte formed by mixing sulfuric acid and the gelling agent has a specific gravity of 1.26 to 1.30, and the battery contains several anode and cathode plates stacked in three layers. Filled in the casing. The colloid electrolyte in each layer is allowed to stand for 2-4 hours, and after filling it is cooled to room temperature, and then the next layer is filled. After all three layers have been filled, the colloid electrolyte is allowed to stand for 5-12 hours, and then the battery is first charged. Lignin sulfonic acid is added into the lead plaster of the cathode plate. The lead of this storage battery
Cathode and anode in the form of antimony grid plate contain 3.5-8% antimony and the calcium content in the grid plate
0.17-0.8%, and the lead content in the anode plate is
5-15% higher.

Another Chinese patent (publication number 2045148)
No. 2) describes a storage battery comprising two layers of colloidal electrolyte, ie, an upper layer and a lower layer, wherein the upper layer is 15 to 22.
% Sodium silicate, 3.0-6.0% silicon dioxide, 1-%
Consists of 2% phosphoric acid and dilute sulfuric acid. The storage battery colloid electrolyte disclosed in Japanese Patent Publication No. 57-58030 consists of 2-10% silicic anhydride and 18-41% sulfuric acid.

GB 2088623A discloses a colloidal electrolyte formed from sulfuric acid and silicon dioxide, wherein the specific surface area of the silicon dioxide is 20-500 m ² / g, preferably 100-200 m2. ² / g and the amount of phosphoric acid is 0.5-15% of the sulfuric acid contained in the colloid electrolyte, preferably 4%.
-6% (weight basis, the same applies hereinafter), and the content of silicon dioxide in this colloid electrolyte is 3-15% (weight basis,
Hereinafter the same), preferably 7-9%.

[0007] Chinese patent 86104708, entitled "Method for producing thixotropic colloid electrolyte" describes a method for preparing an electrolyte containing a silicon-containing gelling agent (sodium silicate, silica sol or amorphous silica powder) and sulfuric acid, The specific surface area of the silica particles of the silica sol used is 50-500 m ²
/ g, preferably 100-300 m ² / g, the colloidal electrolyte comprising 3-15%, preferably 5-15% of silicon dioxide and 30-48%, preferably 35-45% of sulfuric acid. And the temperature in the step of dropping and mixing sulfuric acid into the silica sol is controlled at 10-40 ° C.

A series of problems have been encountered with the silica gel lead-sulfuric acid batteries described in the above-mentioned prior art patents due to the inappropriate concentration of silica sol (as SiO ₂ ) and sulfuric acid in the colloidal electrolyte. For example, large amounts of free dilute sulfuric acid in the filler of the battery can cause significant hydration phenomena, cracks are present in the colloidal electrolyte of the silica gel lead-sulfuric acid battery, and the capacity is rather low, and certain silica gel lead-sulfuric acid batteries The use of sodium silicate as a gelling agent or high concentrations of sodium oxide in silica sols leads to a series of defects,
For example, gelling is too fast, filling is difficult, significant self-discharge occurs, capacity is low, and operating life is short. In some cases, the colloidal electrolyte must be filled in two, three or more parts, and the composition of each part of the filled electrolyte is different, which complicates the manufacturing method. , Resulting in high manufacturing costs and operating inconvenience. In some cases, special isolation goods are provided between the electrodes,
In addition, the special processing of the electrodes makes the production of the battery more complicated, which makes the production cost more expensive and practically difficult.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new type of high-capacity storage battery in which the hydration of the colloidal electrolyte does not easily occur and does not crack, and this new type of silica gel storage battery is for example Large capacity,
It has features such as long operating life, low self-discharge rate, ease of manufacture, no need to place special separator between electrodes, and no special treatment of each electrode,
The purpose is to make this battery easily and widely used at a low price.

It is another object of the present invention to provide a new battery of the type described above and a method for easily producing the colloidal electrolyte used therein at low cost.

[0011]

Colloidal electrolyte of high invention performance [SUMMARY OF] 3 -9.9% of silica sol on the weight of the colloidal electrolyte as 100% (by weight, as SiO _2, hereinafter the same) and 48.1 -75 % Sulfuric acid, the specific surface area of the silicon dioxide particles in the silica sol used is 150-250 m ²
/ g.

[0012] The method of the present invention for producing this high-performance electrolytic solution comprises a step of continuously stirring a silica sol containing SiO ₂ particles having a specific surface area of 150 to 250 m ² / g and sulfuric acid in an acid-resistant reactor. At the same time, maintain the reaction temperature at 20-50 ° C. and maintain 3-9.9% silica sol (as SiO ₂ ) and 4
8.1-Form a colloidal electrolyte containing 75% sulfuric acid (each percentage is expressed as 100%), cool and stir the reaction mixture for another 1-4 hours until the temperature drops below 30 ° C And discharging the obtained colloidal electrolyte from the reactor.

The content (as SiO ₂ ) of silica sol containing SiO ₂ particles with a specific surface area of 150-250 m ² / g in the colloid electrolyte containing an effective concentration of sulfuric acid affects the behavior of the colloid electrolyte. Has been recognized as one of the important factors influencing the silica sol content (SiO ₂
) Directly affects the size of the network pores in the gel. When the content of silica sol in the colloidal electrolyte is lower than 3% and the gel time is longer than 6 hours, a network with large pores and low structural stress is formed, which breaks down during the discharge process. Therefore, no integrated gel can be obtained. During the process of filling such an electrolyte into a lead-acid-silica-gel battery, bubbles may float around the pores of the network and cause significant hydration. On the other hand, the content of silica sol in the colloidal electrolyte is 9.95% (Si
When greater than O ₂ ), a network structure with small pore size and large structural stress is obtained, but the resulting colloidal electrolyte has a high viscosity and a gel time of less than 2 hours Gels rapidly, which results in products that are expensive and have poor thixotropic properties. This colloidal electrolyte is difficult to fill into a battery and can crack during the discharging process even if the filling process is completed. In addition, since the colloid electrolyte has a high silica sol content (as SiO ₂ ) and a small pore size, its resistance increases with the increase of the silica sol content in the colloid electrolyte. The internal resistance of the silica-lead-sulfuric acid battery filled with, increases, while the capacity drops sharply. Therefore, the content of silica sol in the colloid electrolyte is preferably 3-9.
9% is good.

The content of sulfuric acid in a colloid electrolyte containing an effective concentration of silica (as SiO ₂ ) is also an important factor affecting the properties of the colloid electrolyte. When the content of sulfuric acid is lower than 48.1%, the capacity of the silica gel battery after charging is obviously reduced. 75% sulfuric acid content
If it is higher than this, the obtained colloidal electrolyte has a high viscosity and is difficult to fill. After charging of a battery filled with such a colloidal electrolyte, the active material tends to fall off the electrode plate, thereby shortening the operating life of the battery and reducing the starting capacity at low temperatures, Therefore, the content of sulfuric acid in this colloid electrolyte was 48.1 to 75.
% Is preferred.

It must be emphasized that the more important factor affecting the behavior of the colloidal electrolyte is the combined effect of both the concentration of silica sol (as SiO ₂ ) and the concentration of sulfuric acid in the colloidal electrolyte. According to the results of some experiments, one of the important factors affecting various properties of a colloid electrolyte, such as capacity, is 3 to 9.9% (SiO ₂₎ of the above-mentioned silica sol in the colloid electrolyte.
) And sulfuric acid / SiO ₂ ratios (g / g) in each concentration range of 48.1 to 75%. Within the above-mentioned concentration ranges of silica sol and sulfuric acid, the ratio of sulfuric acid / SiO ₂ (expressed in g / g) is 4.5 to 1
A colloid electrolyte of 0.5 gives a large capacity.

In order to further increase the capacity, it is preferable to add aluminum hydroxide to the colloid electrolyte. The content of aluminum hydroxide in this colloid electrolyte (% by weight when the colloid electrolyte is 100%) is preferably 0.1 to 0.5% by weight as aluminum oxide.
Silica sol as one of the starting materials for producing the colloidal electrolyte is 10-30% silicon dioxide, specific gravity 1.060-
It is a commercial product having a pH of 1.22 and a pH of 8-9.5.
The content of sodium oxide in the silica sol is 0.2-
0.4%. When the amount of sodium oxide is higher than 0.4%, the obtained colloidal electrolyte shows a high self-discharge rate and rapid gelation after filling in a storage battery, and thus the content of sodium oxide in the silica sol is low. The lower the better. The concentration of iron in the silica sol is preferably 0.0
It should be lower than 03%, and the lower the better. When the iron content in the silica sol is high, a high self-discharge rate may be obtained. When the content of silicon oxide in a commercially available silica sol is high, it may be diluted with pure water to a suitable concentration as a starting material for producing this colloid electrolyte. The pure water used in the present invention is preferably desalinated water having a specific resistance higher than 2 × 10 ⁵ Ω · cm. The higher the specific resistance of the demineralized water, that is, the purer, the better.

The sulfuric acid used is sulfuric acid for storage batteries, industrial sulfuric acid,
Either analytical purity (AP) sulfuric acid or chemical purity (CP) sulfuric acid may be used. Concentrated sulfuric acid can be used as a starting material for the preparation of the colloidal electrolyte, which can also be diluted with pure water to a suitable concentration that is easy to add. Various aluminum salts to prepare aluminum hydroxide (e.g. aluminum chloride, aluminum sulfate and aluminum nitrate, etc.) is added to the water, to precipitate the aluminum ions as aluminum hydroxide, filtered, and Cl ^-, SO ₄ ^- Or washing with hot water until NO ₃ ^- ions are no longer detectable, then adding an effective amount of this aluminum hydroxide to the silica sol with stirring to reduce the aluminum hydroxide content in the resulting colloidal electrolyte to 0.1.
-0.5% (as aluminum oxide).

SiO ₂ particles having a specific surface area of 150-250 m ² / g
The silica sol containing 10-30% and sulfuric acid are simultaneously placed in an acid-resistant reactor (eg, a three-neck glass flask, an acid-resistant reactor, etc.), and the reaction temperature is controlled at 20-50 ° C. The acid resistant reactor may be cooled with cold water, ice water or salt / ice water to control the reaction temperature at 20-50 ° C. The results of some experiments show that greater than 50 ° C. release of acid gases releases the reaction temperature, corrodes the equipment and hinders operation. In addition, if the time to hold the colloid electrolyte at a temperature above 50 ° C. is too long, the thixotropy and stability of the product tend to be impaired. On the other hand, when the reaction temperature is lower than 20 ° C., the feeding rate becomes too slow. Therefore, the reaction temperature is preferably 20
-It is better to control to 50 ℃. Feeding times are generally controlled within 1-3 hours, and cooling and stirring times are generally 1-4 hours.
Time (the continuous cooling and stirring time is the time interval from when the feed is stopped to when the temperature of the reaction mixture is cooled to below 30 ° C.), whereby
-9.9% silica sol (as SiO ₂ ) and 48.1-75
% Sulfuric acid, and preferably the H ₂ SO ₄ / SiO ₂ ratio (g / g) is within this silicon dioxide and sulfuric acid content range.
4.5 to 10.5.

A sample is withdrawn from the reaction mixture and examined for its sulfuric acid content and whether the silicon oxide content matches the prescribed composition, and if not, the mixture is adjusted by adding sulfuric acid, silica sol or demineralized water. The reaction mixture was cooled and stirred for another 1-2 hours, and the reaction mixture was cooled to 30 ° C.
The reaction product is removed from the reactor after it has cooled to a lower temperature. If the analyzed content of sulfuric acid and silicon dioxide in the analytical sample matches that of the desired composition, the product can be removed from the reactor after it has been cooled to below 30 ° C.

The appearance of the obtained colloidal electrolyte is milky white, the specific gravity is 1.32 to 1.35, the gel time is 2 to 4 hours, and the operating life is about 2 to 3 years. The analysis method used in the method of the present invention uses gravimetric analysis for silicon dioxide, turbidimetric analysis using silver nitrate for chloride ion, turbidimetric analysis using barium chloride for sulfate ion, and ammonium ammonium sulfocyanide titration for iron. Flame photometry or atomic absorption spectroscopy for sodium oxide.

The silica particle size and specific surface area of the silica sol are determined by the following methods known to those skilled in the art. That is, a certain amount of sample is added to a 20% aqueous solution of sodium chloride,
Titrate to pH 9 with N NaOH. NaO consumed
Record the volume of H solution and calculate according to the following formula:

[0022]

(Equation 1)

In this equation, S is the specific surface area of the sample in m ² / g V is the consumption in ml of NaOH solution N is the equivalent concentration of NaOH solution 25 is the correction factor of the above empirical formula.

In order to calculate the particle size from the specific surface area, the following equation is used: As = K / S, where As is the diameter S of the colloid particles expressed in mμ and S is the specific surface area expressed in m ² / g of the colloid particles. K is a constant and is 2720.

As shown in FIG. 1, the large-capacity colloidal storage battery of the present invention comprises a battery casing (1), an anode plate (2),
Cathode plate (3), separator (4), connecting rod for anode (5), connecting rod for cathode (6), injection hole for liquid filling (7), battery cover (8), and novel electrolyte of the present invention (9) and a connection plate (10), a buffer means (11), and an acid mist treatment means (12). The colloidal electrolyte (9) used in the battery according to the invention is made by the method described above and comprises 3-9.9% (by weight, hereinafter the same) silica sol (SiO ₂ , same hereafter) and 48.1-74%. Contains sulfuric acid.

The battery casing (1) of the storage battery of the present invention is generally made by press-molding a material selected from the group consisting of ABS resin, polypropylene resin, bakelite and hard rubber. This is also the anode plate (2), the cathode plate
(3), separator (4), connecting rod for anode (5), connecting rod for cathode
(6), a liquid filling injection hole (7) (a gas permeable cover may be provided above this injection hole to allow gas to pass through) and a battery cover (8) Instead of the solution, the colloidal electrolyte of the present invention is used.

In the large-capacity colloidal storage battery of the present invention, since the colloidal electrolyte is used instead of the dilute sulfuric acid electrolyte, the amount of acid mist released during use for floating charging is as follows: 50 -60 compared to that of
%Decrease. It is another object of the present invention to provide a buffer means (11) mounted on the top of the battery, which further reduces the amount of acid mist released from the battery during floating charging. Can be. The buffer means (11) is a piece of an acid-resistant compressible material selected from the group consisting of a polyether-type polyurethane foam resin, a polyester-type polyurethane foam resin, and a porous rubber. Preferably, the size of the piece of resin material is suitable for placement in the battery and its thickness should be 3-15 mm. The mounting location is the top inside the battery and the bottom of this piece of resin material is in contact with the colloid electrolyte (9). The buffering means has three functions: 1) Makes the colloid electrolyte contain an appropriate amount of water and prevents water from evaporating from the colloid electrolyte.

2) When a small amount of dilute sulfuric acid is formed in the colloid electrolyte of the colloid storage battery, the buffer means (11) removes the dilute sulfuric acid (ie, a mixture of sulfuric acid and water) into the pores of the foam. When the colloid electrolyte in the battery dries and needs moisture, releasing the dilute sulfuric acid absorbed in the pores of the foam, thus causing cracking of the colloid electrolyte. prevent. Therefore, this buffer means provides a buffering action and can be considered as a buffer layer.

3) The buffer means can absorb and remove about 50% of the emission of acidic mist from the colloidal electrolyte while the colloidal battery is used for floating charging, ie, the buffer means Due to the attachment, while the storage battery of the present invention is used for floating charging, the amount of acid mist released from the storage battery is only about 2% of the amount released from the storage battery using dilute sulfuric acid as the electrolyte.
5%, ie 75% of the acid mist is removed.

In order to eliminate any release of acid mist from the storage battery of the present invention during use in floating charging, a means for treating acid mist is provided in the liquid filling inlet (7) (gas permeable means). More preferably, (instead of the cover). The means for treating the acid mist is a small cylindrical means with a cover on top, with several (typically 6 to 16) perforations around the cover as gas outlets. The cover is screwed to the cylindrical means and the bottom of the cylindrical means is likewise screwed to the liquid filling inlet (7). The cylindrical means has a bottom with a hole in the center at the bottom, into which a tube 1/5 to 1/3 of the height of the cylindrical means is inserted and connected to the inside of the storage battery. Have been. N inside this cylinder
It is filled with a foam material selected from a polyether polyurethane foam resin and a polyester polyurethane foam resin impregnated with an aOH solution. The concentration of this sodium hydroxide is generally between 5 and 20% by weight. This means can be made by pressing from polymethyl methacrylate, polyvinyl chloride or bakelite. The remaining acidic mist that permeates the buffer means and enters the cylindrical means via the tube at the bottom of the cylindrical means is absorbed and neutralized by the sodium hydroxide in the foam.
The resulting water flows to the bottom of the cylindrical means, so that the acid mist is completely removed. More details on Wang Liang-xiang
And the like in Chinese Patent Application No. 9020357.1.

The colloidal electrolyte used in the accumulator according to the invention is filled as follows: The colloidal electrolyte, which has been stored in a gel-like and stationary manner for a long time in a plastic bucket, is again restored to its original form. Shake vigorously (preferably with an electric motor) for several tens of seconds until fluidity is restored and the absence of small particles is confirmed. This is placed in a storage battery casing not filled with dilute sulfuric acid, preferably 10
-Slowly fill to 15 mm above filling level. The storage battery filled with the colloid electrolyte is allowed to stand still for 4-6 hours. After the colloidal electrolyte is essentially stable, the charging process can be performed according to the methods described in the battery operation manual. The method of charging is the same as that used in lead-sulfuric acid batteries using dilute sulfuric acid as the electrolyte, except that an effective amount of demineralized water must be added so that dry charging is strictly prevented.
After the charging process has been completed, the buffer is fitted and an effective amount of water can be added so that the buffer can maintain moisture for a long time.

The present invention has the following various advantages: The large-capacity colloidal battery of the present invention has various advantages as compared to a battery using dilute sulfuric acid as an electrolyte: a) The large-sized colloidal battery of the present invention completely eliminates the emission of acid mist during floating charging. , Thereby preventing environmental pollution, protecting worker's health and providing safe and good work. The release of flammable and explosive hydrogen and oxygen gases is reduced by about 56% compared to that released from dilute sulfuric acid batteries, thus preventing explosion accidents.

(B) The large-capacity colloidal storage battery of the present invention does not cause acid leakage or overflow, and does not cause acid leakage even when tilted at an angle of 90 ° (about 48.5 in the case of dilute sulfuric acid storage battery). (Leakage occurs when tilted at an angle of °), thus preventing corrosion of other materials and saving costs for corrosion-resistant equipment. The insulation against the ground is 0.5 V in the case of the lead-sulfuric acid battery, and 0.25 V in the case of the large-capacity storage battery of the present invention, the insulation performance is good, and the insulation of the battery is improved by 50%. To prevent the occurrence of electric sparks and thus solve a problem that has been unresolved for many years.

C) The high-capacity colloidal battery of the present invention shows low corrosivity, good low-temperature resistance and slight self-discharge. D) The surface of the large-capacity colloidal battery of the present invention is always kept normal, and the number of times of adding the additional demineralized water is reduced by 50% or more as compared with the case of the dilute sulfuric acid battery, that is, six months. Demineralized water only needs to be added once, and the required amount of demineralized water is 2/3
Also decrease. Although the lead-sulfuric acid battery needs to be repaired once every six months, the large-capacity colloidal battery according to the present invention has been operating normally without maintenance for more than three years, thus greatly reducing the amount of maintenance work.

E) The operating life of the large-capacity colloidal battery of the present invention is extended by 100% or more as compared with that of the sulfuric acid battery. 2. The high-capacity colloidal battery of the present invention has the following advantages over the colloidal battery according to the prior art: a) Completely eliminating the emission of acid mist, thereby preventing environmental pollution and protecting the health of workers. You.

B) The large-capacity storage battery of the present invention has a larger capacity than the colloid storage battery of the prior art, and is close to the capacity of the lead-sulfuric acid storage battery. According to international standards for the nominal capacity of the discharge at 20 hours, the average capacity of the large capacity battery of the present invention is equal to that of the lead-sulfur battery of the same type.
%, And the maximum capacity can reach up to 91.6% of that of lead-sulphur batteries.

(C) The large-capacity colloid storage battery of the present invention has better starting performance than other colloid storage batteries,
It is close to that of a lead-sulfuric acid battery and is therefore particularly suitable for starting under high power. In a comparative test conducted on a boat, one set (four) of the large-capacity colloidal batteries of the present invention and another set (four) of lead-sulfuric acid batteries were used for starting the main engine and for emergency lighting. The results show that the startability of the main engine can meet the requirements for lead-sulfuric acid batteries. Under the condition that the main engine is started 8-10 times daily, the battery is still in good working condition, which is twice as long operating life despite showing the same performance as lead-sulfuric acid battery Has been shown. Furthermore, in a start-up test of a car performed in an extremely cold region, the storage battery of the present invention shows a good startability even at a temperature of -40 ° C.

D) The large-capacity colloid storage battery of the present invention
1.28 V start-up performance and 6.3 A charge tolerance (6.0 A
And no substantial voltage drop during discharge at 120 A / 3 seconds, with an operating life of 3 years or more, low self-discharge, after the first charge The degree of hydration is low, the gel time is 2-4 hours, and does not crack or hydrate during practical use.
It is suitable for quick charging, and working capacity can be reached in less than 2-2.5 hours.

E) The large-capacity colloid storage battery of the present invention requires only one filling step, which is inexpensive, easy to operate, and can be used for a wide range of applications.
It can be used with great economic benefits in automobiles, ships, electric vehicles, aircraft, underground headlamps, emergency lights and computers and the like. For example, according to an evaluation of a fishing company's ship repair factory, the cost can be reduced by more than 1.3 million yuan per year by using the large-capacity storage battery of the present invention. The social benefits provided by the prevention of environmental pollution and the prevention of equipment corrosion are even less appreciable.

[0040]

EXAMPLES The following examples are provided to further illustrate the present invention, but do not limit the technical scope of the present invention in any way. It should be understood that they are defined only by the claims. Example 1 A large-capacity colloidal battery according to the present invention has a battery casing.
(1), anode plate (2), cathode plate (3), separator (4), connecting rod for anode (5), connecting rod for cathode (6), filling hole for liquid filling (7), battery cover ( 8), novel electrolyte of the present invention (9), connecting plate
(10), buffer means (11) and means for treating acid mist (12)
Consisting of Buffer means (11) and means for treating acid mist
Except for (12), other structures and components thereof and methods of making them are well known to those skilled in the art. Battery casing (1) is A
Made of BS resin. Storage battery using are those that do not fill the dilute sulfuric acid, comprising the filled colloidal electrolyte (as SiO ₂₎ 6.0% of the silica sol and 55% sulfuric acid, the ratio of sulfuric acid / silicon dioxide (g / g) is 9.16 It is. It has a 90% capacity and is suitable for battery discharge at high power. Buffer means attached to the inside top of this battery
(11) is a piece of a polyester-type polyurethane foam resin having a thickness of 5 mm. The bottom of the foamed resin is in contact with the colloid electrolyte (9). The battery does not hydrate or crack during use. The emission of acid mist during floating charging is only 23% of that emitted from the same type of lead sulfate battery. The amount of hydrogen and oxygen gases released during floating charging is only 44% of that released from the same type of lead sulfate battery. Example 2 This example shows that not only the buffer means (11) is attached to the inner top of the battery, but also the means for treating acid mist (1).
2) is substantially the same as Example 1 except that it is provided at the filling injection hole (7) of the battery. The tube in the means for treating acidic mist is 1/4 of the height of the cylindrical means.
Having a length of The means (12) made of polyester-type polyurethane foam resin is impregnated with a 10% strength NaOH solution. Acid mist released during floating charging is completely eliminated, thereby preventing environmental pollution. The amount of hydrogen gas and oxygen gas released is only 45% of that of a lead-sulphur battery of the same type. Example 3 This example shows that the filled colloidal electrolyte contains 7.0% silica sol (as SiO ₂ ) and 48.5% sulfuric acid, and the sulfuric acid / silicon dioxide ratio (g / g) is 6.93.
And substantially the same as Example 1 except that the capacity is 88%. The amount of acid mist released during floating charging is slightly less than that released from lead-sulfur batteries of the same type.
23.5%. Example 4 This example shows that the filled colloidal electrolyte contains 9.9% silica sol (as SiO ₂ ) and 60% sulfuric acid, and the sulfuric acid / silicon dioxide ratio (g / g) is 6.06, and the capacity is Substantially the same as Example 1 except that the amount of acid mist released during floating charging is about 86% and is only 25.1% of that released from the same type of lead sulfate battery. . The amount of hydrogen gas and oxygen gas released during floating charging is 45.1% of that released from the same type of lead-sulfur battery. Example 5 This example includes a silica sol colloid electrolytic solution filled is 5% and (as SiO ₂₎ 52% sulfuric acid, and sulfuric acid /
The ratio of silicon dioxide (g / g) is 10.4 and the capacity is about 88% and the amount of acid mist released during floating charging is only a fraction of that released from lead-sulphur batteries of the same type. Substantially the same as Example 1 except that it is 25.1%. The amount of hydrogen gas and oxygen gas released during floating charging depends on the amount of
42.9%. Example 6 This example is substantially the same as Example 5 except that the loaded colloidal electrolyte also contains 0.3% aluminum oxide and the capacity is 91.6%. The amount of acid mist released during floating charging is only 24.8% of that released from the same type of lead sulfate battery. The amount of hydrogen gas and oxygen gas released during floating charging is 42.2% of that released from the same type of lead-sulfur battery. Example 7 In an acid-resistant reactor, having a specific surface area of 210 m ² / g, 0.25
Specific gravity pH 8.5 containing SiO ₂ particles of 21% containing sodium oxide and less iron than 0.003% of% 1.13
Commercial silica sol and sulfuric acid (including 77.03% H ₂ SO ₄ )
Was charged simultaneously as starting material. The reaction temperature was controlled at 45 ° C. by cooling with ice water, whereby (as SiO ₂₎ SiO ₂ sol include 6.0% and _{H 2 SO 4 55.0%, H} 2
A colloidal electrolyte having a SO ₄ / SiO ₂ ratio (g / g) of 9.16 was obtained. The water used to dilute the silica sol and sulfuric acid has a specific resistance of 250,000 Ω · cm. The feed was completed within about 2 hours, then cooled and stirred for an additional 2.5 hours. The resulting colloidal electrolyte was milky white and had a specific gravity of 1.35, which was removed from the reactor after its temperature had cooled to 27 ° C. This colloidal electrolyte has a gel time of 2 hours in the filled battery and can be stored for 2.5 years without hydration or cracking. Filled in a new storage battery that has never been filled with sulfuric acid electrolyte, this colloidal electrolyte is suitable for discharging a battery with high power and has a capacity of about 90%. Example 8 The method and conditions used in this example are as follows: pH 9.0 containing a specific surface area of 180 m ² / g as starting material and containing 14% of SiO ₂ particles containing 0.2% sodium oxide and less than 0.003% iron. Silica sol with specific gravity of 1.09 and H ₂ SO ₄
Using sulfuric acid containing 97.0%, the reaction temperature was kept at 44 ± 1 ° C., thereby (as SiO ₂₎ sol 7.0% and
H ₂ SO ₄ containing 48.5%, H ₂ SO ₄ / SiO ₂ ratio (g / g)
Substantially the same as in Example 7, except that a colloidal electrolyte that was 6.93 was obtained. The feed was completed within about 3 hours, then cooled and stirred for an additional 2.5 hours. The resulting colloidal electrolyte has a specific gravity of 1.35 and a gel time of 3 hours in the charged battery, and can be stored for 2.5 years without hydration or cracking,
It has a capacity of about 88%. Example 9 The method and conditions used in this example are as follows: pH 9.5 containing specific surface area 195 m ² / g as starting material and containing 29.7% of SiO ₂ particles with 0.25% sodium oxide and less than 0.003% iron. Silica sol with specific gravity of 1.19 and H ₂ S
The reaction temperature is controlled at 47 ± 1 ° C. using sulfuric acid containing 87.37% of O ₄ , whereby it contains 9.9% of silica sol (as SiO ₂ ) and 60.0% of sulfuric acid, and the ratio of sulfuric acid / silicon dioxide (g / g)
g) except that we obtained a colloidal electrolyte with 6.08
Substantially the same as in Example 7. The mixture was further cooled and stirred for 3.5 hours. The resulting colloidal electrolyte has a specific gravity of 1.35 and a gel time of 2 hours in the filled battery, can be stored for 2 years without hydration or cracking, and has a capacity of about 86%. Example 10 The method and conditions used in this example are as follows: a starting material having a specific surface area of 240 m ² / g and a pH of 9.0 containing 0.20% of sodium oxide and 15% of SiO ₂ particles containing less than 0.003% of iron. Silica sol with specific gravity of 1.092 and H
_The reaction temperature was controlled at 46 ± 1 ° C. using sulfuric acid containing 78% ₂ SO ₄ , whereby it contained 5% silica sol (as SiO ₂ ) and 52% sulfuric acid, and the ratio of H ₂ SO ₄ / SiO ₂ (g / G) is 1
Make a colloid electrolyte that is 0.4, cool and stir for an additional 3.0 hours, the resulting colloid electrolyte has a specific gravity of 1.33, a gel time of 2 hours in the filled battery, and cause hydration and cracking Storage for about two years without having about 88% capacity,
Substantially the same as in Example 7. Example 11 The methods and conditions used in this example, except that this was added aluminum hydroxide to contain 0.9% of Al ₂ O ₃ in the silica sol of the starting material, is substantially the same as in Example 10. The obtained colloidal electrolyte is 0.3% A
It contains l ₂ O ₃ and has a capacity of 91.6%. Example 12 The method and conditions used in this example are as follows: pH 8.4 containing 185 m ² / g of specific surface area as starting material and containing 20% of SiO ₂ particles containing 0.28% sodium oxide and less than 0.003% iron. Silica sol with specific gravity of 1.126 and H
₂ SO _{4 Use} sulfuric acid containing 96.03% and set the reaction temperature to 43 ± 1 ℃
9.9% silica sol (as SiO ₂ )
And H ₂ SO ₄ / SiO ₂ ratio (g / g
g) is substantially the same as in Example 7, except that a colloidal electrolyte having a g of 4.9 was prepared and further cooled and stirred for 2.5 hours. The resulting colloidal electrolyte has a specific gravity of 1.34 and a gel time in the charged battery of about 2 hours, and can be stored for more than 2 years without hydration or cracking, and has a capacity of about 86%. Have. Example 13 The procedure and conditions used in this example are such that the silica sol starting material contains 30% SiO ₂ and has a specific gravity of 1.21 and the starting sulfuric acid contains 100% H ₂ SO ₄ and the reaction temperature is reduced. 49 is controlled to ± 1 ° C., thereby (as SiO ₂₎ silica sol containing 9.0% and 70% sulfuric acid, H ₂ SO ₄ / SiO
Substantially the same as in Example 12, except that a colloidal electrolyte having a ratio of ₂ (g / g) of 7.78 was obtained. The feeding time is 3 hours, then cooling and stirring for another 3.5 hours and the resulting colloidal electrolyte has a specific gravity of 1.3
5 and 86% capacity.

[Brief description of the drawings]

FIG. 1 is a partially cutaway perspective view of a specific example of a large-capacity colloid storage battery according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Battery casing 2 Anode plate 3 Cathode plate 4 Separation plate 5 Anode connection rod 6 Cathode connection rod 7 Injection hole for liquid filling 8 Battery cover 9 Colloid electrolyte 10 Connection plate 11 Buffer means 12 Acid mist treatment means

──────────────────────────────────────────────────の Continued on the front page (73) Patent holder 591239036 Shuo Zhen SHUO ZHENG Dalian Lushuen Quo District Chang Zuan Road Nanea Rain 12 Room 101 (73) Patent holder 591239047 Han Zen HANG ZHENG Dalian Rushuen Cuo District Changzhang Road Nanea Rain 12 Room 101 (72) Inventor Lian Kien Wan, Republic of China Dalian Rushuen Quo District Changzhang Road Nanea Rain 12 Room 101 (72) Inventor Anchen Zhen, China Darian Rushuen Quo District Chang Juan Road Nanea Rain 12 Rooms 101 (72) Akira Shao Zhen Zen China Darian Rusuen Quo District Chang Zuan Road Nanea Rain 12 Room 101 (72) Inventor Han Zen China Dalian Rushuen Quo District Chang Zuan Road Nanea Rain 12 Room 101 (56) References JP Showa 52 JP-147739 (JP, A) JP-A-63-221565 (JP, A) JP-A-61-256565 (JP, A) JP-A-56-114288 (JP, A) JP-A-47-32326 (JP, A) JP-A-1-144571 (JP, A) JP-A-3-57165 (JP, A) JP-A-63-237365 (JP, A) JP-A-60-165045 (JP, A) 172464 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , DB name) H01M 10/06-10/16 H01M 2/12

Claims (17)

(57) [Claims] 1. A large-capacity storage battery including a battery casing, an anode plate, a cathode plate, a separator, and an electrolyte, wherein the electrolyte is substantially a) 3 to 9.9% (% by weight, Same) silica sol
(As SiO _2), b) 48.1 to 75% sulfuric acid, and c) 15.1 to consisting 48.9% of water, high capacity colloidal storage battery. 2. The high-capacity colloid storage battery according to claim 1, wherein the sulfuric acid / silicon dioxide (g / g) is 4.5 to 10.5 within the concentration range of the sulfuric acid and silicon dioxide. 3. The silica sol has a specific surface area of 150 to 250 m / g.
The large-capacity colloid storage battery according to claim 1, comprising silica particles having 4. The high-capacity colloid storage battery according to claim 1, wherein said electrolyte also contains 0.1 to 0.5% of aluminum hydroxide, wherein the total amount of said aluminum hydroxide is converted to aluminum oxide. 5. The large capacity colloid storage battery according to claim 1, further comprising a buffer means. 6. The high-capacity colloidal storage battery according to claim 5, wherein the buffer means is attached to the inside top of the storage battery. 7. The large-capacity colloid storage battery according to claim 6, wherein the bottom of said buffer means is in contact with a colloid electrolyte in the storage battery. 8. The cushioning means is made of a piece of compressible acid-resistant foam resin and has a thickness of 3 to 5 m.
7. The large-capacity colloid storage battery according to claim 6, wherein m is m. 9. The high-capacity colloid storage battery according to claim 1, wherein the electrolyte contains 0.4% by weight or less of sodium oxide. 10. The large capacity colloid storage battery according to claim 1, wherein said electrolyte contains less than 0.003% by weight of iron. 11. The large-capacity colloid storage battery according to claim 1, wherein a means for treating acid mist is attached to an injection hole for filling the storage battery with a liquid. 12. The method for producing a thixotropic colloid electrolyte used in a large-capacity colloid storage battery according to claim 1, comprising the following process steps: a) preparing an aqueous sulfuric acid solution having an appropriate concentration from sulfuric acid and water; B) the aqueous sulfuric acid solution and silica sol prepared in step a) above are added dropwise to the acid-resistant reactor at a temperature of 20-50 ° C. with continuous stirring, and c) the reaction mixture is further added for 1-4 hours Stir and cool until the temperature of the mixture drops below 30 ° C., whereby silica sol (as SiO ₂ ) 3 to 9.9%
(Wt%), 48.1 to 75% sulfuric acid, and 15.1-4
Forming a colloidal electrolyte comprising 8.9% water. 13. The silica sol has a specific surface of 150 to 250 m ² / g.
13. The method of claim 12, comprising silica particles having the formula: 14. Sulfuric acid / silicon dioxide (g / g) is 4.5 to 10.5 in each concentration range of said sulfuric acid and silicon dioxide.
13. The method of claim 12, wherein 15. The method of claim 12, wherein the electrolyte comprises less than 0.4% by weight of sodium oxide and less than 0.003% of iron. 16. The content of aluminum hydroxide (Al ₂ O) in the obtained colloidal electrolyte while stirring the silica sol.
13. The method of claim 12, wherein an amount of aluminum hydroxide effective to bring 0.1) to 0.5% by weight (converted to ₃ ) is added. 17. The colloidal electrolyte consisting of 3 to 9.9% silica sol (as SiO ₂ ), 48.1-75% sulfuric acid and 15.1-48.9% water is created by the added silica sol and aqueous sulfuric acid solution; 13. The method of claim 12, wherein the ratio of sulfuric acid / silicon dioxide (g / g) is 4.5-10.5 within each of the silica sol and sulfuric acid concentrations.