CN1049530C

CN1049530C - Pasty colloid accumulator and its mfg. method

Info

Publication number: CN1049530C
Application number: CN92104882A
Authority: CN
Inventors: 王振川
Original assignee: Individual
Current assignee: Individual
Priority date: 1992-06-22
Filing date: 1992-06-22
Publication date: 2000-02-16
Anticipated expiration: 2007-06-22
Also published as: CN1081025A

Abstract

The present invention discloses an improved lead-acid accumulator and a manufacturing method thereof. The improvement of the present invention lies in providing a paste colloid electrolyte containing diluted sulfuric acid whose specific gravity is 1.40, plaster of paris and alkyd varnish. The present invention mainly solves the problem that the electrolytic solution of the existing lead-acid accumulator spills out. The accumulator of the present invention is especially suitable for automobiles, steamships, airplanes and naval vessels.

Description

Pasty colloid accumulator and its manufacturing method

The present invention relates to a lead-acid battery for storing and supplying electric energy by utilizing reversible electrochemical reaction and its manufacturing method, in particular, it relates to a lead-acid battery containing pasty colloid electrolyte and its manufacturing method. According to IPC classification table, the invention belongs to

H₀IM_10/06。

Lead-acid batteries are widely used in automobiles, ships, airplanes, and naval vessels. The existinglead-acid battery is mainly composed of a polar plate, a clapboard, a container and electrolyte. The electrode plate comprises a positive plate and a negative plate, and the active material filled in the grid frame grids of the positive plate is lead dioxide (PbO)₂) The active material filled in the grid of the negative plate is spongy pure lead (Pb). A plurality of positive plates (such as 4-13 plates) and a plurality of negative plates (such as 5-14 plates) are respectively connected by two transverse plates to form a positive plate group and a negative plate group. The transverse plate is provided with electricityAnd gaps are reserved among the piles. The positive and negative plates in the positive and negative plate group are alternated and embedded with each other, and a partition plate is inserted between each pair of positive and negative plates, so that a plurality of unit cell groups are formed. The separator should both be insulating and ensure free penetration of the electrolyte, for example made of porous wood material, plastic material. The container of the lead-acid storage battery is made of an acid-resistant, heat-resistant and shock-resistant material (such as a hard rubber), and a plurality of unit cells are mounted together. And each single cell is covered with a cover, and the cover is provided with a hole for leading out an electric pile and filling distilled water and electrolyte. The electrolyte in current lead-acid storage batteries is pure sulfuric acid (H)₂SO₄) And distilled water (H)₂O) is mixed according to a certain proportion to form a solution. Active material PbO on positive and negative plates during charging and discharging of the storage battery₂And Pb and H in the electrolyte₂SO₄Reversible chemical reactions occur:

put by Thus, during discharge of the battery, the sulfuric acid in the electrolyte gradually decreases and the water gradually increases. That is, in the lead-acid storage battery, the water content in the storage battery container is more and more, and the fluidity of the electrolyte containing sulfuric acid is more and more increased. If the battery container is not tightly closed, the electrolyte in liquid form is easily spilled, and the sulfuric acid in the electrolyte can often be dangerous to workers or equipment near the battery. Meanwhile, the amount of sulfuric acid participating in chemical reaction is reduced due to the splashing of the electrolyte, and the service time of the lead-acid storage battery is shortened. These disadvantages of lead-acid batteries are particularly pronounced in vehicles that are often in a bumpy state (e.g., automobiles, ships, airplanes, ships), and the consequences thereof are even more severe. Lead-acid batteries have another serious disadvantage. I.e. active material PbO on positive and negative plates₂And no protective layer is arranged outside Pb, so the Pb easily falls off. Lead-acid batteries generally have a short service life of only 2 to 3 years.

In order to overcome the problem of electrolyte splashing of lead-acid batteries, lead-acid batteries using colloidal electrolytes are commonly used in the prior art. Namely, purified sodium silicate solution is added into sulfuric acid aqueous solution. After the sodium silicate solution and the sulfuric acid aqueous solution are mixed, they are coagulated into a thick substance, i.e. colloid. The electrolyte is colloidal, so that the electrolyte does not flow, does not splash out, and does not corrode human bodies or equipment. However, the colloid electrolyte storage battery has two disadvantages: firstly, the resistance of the colloidal electrolyte is larger than that of the sulfuric acid electrolyte, so that the internal resistance of the storage battery is increased and the capacity of the storage battery is reduced. For example, the starting capacity at normal temperature is only 80% of that of a normal battery, and the starting capacity at low temperature is only 50% of that of a normal battery; secondly, the contact between the colloidal electrolyte and the polar plate is not uniform, which can cause serious self-discharge which is much larger than that of the common storage battery.

It is an object of the present invention to overcome the above-mentioned deficiencies of the prior art by providing an improved pasted colloidal lead-acid battery which does not spill electrolyte and which does not significantly reduce the capacity of the battery;

it is another object of the present invention to provide a method for manufacturing said pasted colloidal lead-acid storage battery.

In order to achieve the first object of the present invention described above, according to the present invention, there is provided a paste-like colloidal lead-acid storage battery comprising:

a positive electrode plate group consisting of a plurality of positive electrode plates filled with active material PbO₂The positive electrodes are connected by a transverse plate with an electric pile;

a negative electrode plate group consisting of a plurality of negative electrode plates filled with an active material Pb and connected by another transverse plate with another electric pile, each of said negative electrode plates being alternately fitted to each of said positive electrode plates of said positive electrode plate group;

a plurality of separators made of a porous insulating material interposed between each pair of the positive and negative electrode plates;

a housing container for housing said positive and negative electrode plate sets, said separator and electrolyte; and

an electrolyte injected into the container, the electrolyte comprising dilute sulfuric acid having a specific gravity of 1.40, plaster of Paris (A), (B), and (C)

) And the alkyd varnish, wherein the volume ratio of the three is as follows in sequence:

(2-3)∶(0.7-1.5)∶(0.3-0.8)；

according to the best embodiment of the invention, the volume ratio of the dilute sulfuric acid to the plaster and the alkyd varnish is as follows:

2.5∶1.0∶0.4。

in order to achieve the second object of the present invention, according to the present invention, there is provided a method for manufacturing said pasted colloidal lead-acid storage battery, which comprises the steps of, in order:

a. preparing an electrolyte containing dilute sulfuric acid, plaster of paris and alkyd varnish with the specific gravity of 1.40, wherein the volume ratio of the dilute sulfuric acid to the plaster of paris to the alkyd varnish is as follows in sequence:

(2-3)∶(0.7-1.5)∶(0.3-0.5)；

b. injecting said prepared electrolyte into said container containing said positive and negative electrode plate groups and said separator;

c. cooling said housing container filled with said electrolyte to below 15 ℃;

d. initial charging: charging with 1/10 rated current for 1-3 hr, adding reduced electrolyte, charging with 1/20 rated current for 40 min, and finishing the initial charging step.

According to the preferred embodiment of the production method of the present invention, the volume ratio of dilute sulfuric acid having a specific gravity of 1.40, plaster of Paris, and alkyd varnish in the electrolyte is 2.5: 1.0: 0.4 in this order.

Since the main improvement of the invention lies in the electrolyte itself, and not in the other components of the battery: positive and negative electrode plate groups, a separator and a container. These components of the battery are well known, and therefore, they are not described in detail in this specification, and it is not necessary to draw their structural diagrams.

The present invention will be described in more detail below with reference to examples of the present invention.

Firstly, diluting sulfuric acid with distilled water to specific gravity of 1.40, and taking 2-3 parts (by volume) of diluted sulfuric acid with specific gravity of 1.40, preferably 2.5 parts (by volume, the same applies below); then slowly pouring 0.7-1.5 parts of plaster of paris, preferably 1.0 part of plaster of paris, by volume into the dilute sulfuric acid, and lightly stirring by using a glass rod or a wooden stick to ensure that the foam on the surface of the plaster of paris is gradually reduced and is not blocked; then, slowly pouring 0.3-0.8 parts of alkyd varnish, preferably 0.4 parts of alkyd varnish into the mixed solution of dilute sulfuric acid and plaster and quickly stirring (taking care to prevent splashing) until the mixture is in a porridge shape; thus, the pasty colloidal electrolyte used for the secondary battery of the present invention was produced;

next, said paste-like colloidal electrolyte is immediately injected into a container of said secondary battery comprising said positive and negative electrode plate groups and said separator. When the injection is started, electrolyte gaps may exist in each single cell, so that the shell container needs to be knocked down on an elastic plate (such as a rubber plate),then the height difference of the lacking electrolyte is complemented, and the injection is finished;

then, cooling said housing filled with said electrolyte to below 15 ℃;

and finally, carrying out initial charging. The initial charge is carried out in two steps. In the first step, firstly, 1/10 current with rated capacity is used for charging for 1-3 hours. During initial charging, the temperature of the shell container is gradually increased to about 40 ℃, a large number of bubbles are emitted from the container at the beginning, and finally the bubbles are gradually reduced, so that the voltage of the storage battery is kept basically unchanged. Because the electrode plate absorbs partial acidity, the electrolyte is solidified and thickened, the volume of the electrolyte is slightly reduced, and the damaged electrolyte is compensated after cooling. Typically, the height of the electrolyte is 2-3cm higher than the plate stack. But not too full, otherwise electrolyte overflow is likely to occur during normal use. The second step of the initial charge is to charge with 1/20 rated capacity current for about 40 minutes. The upper and lower temperatures of the battery should be substantially the same. After the initial charging, the storage battery can be put into use.

According to the above-mentioned preparation steps of said invention the paste colloid lead-acid accumulator conforming to said invention can be made; in other words, the battery according to the present invention is manufactured according to the manufacturing steps of the method of the present invention described above.

For example, dilute sulfuric acid with the specific gravity of 1.40, plaster of paris and alkyd varnish are prepared into paste colloid electrolyte according to the volume ratio of (2-3) to (0.7-1.5) to (0.3-0.8), and the paste colloid electrolyte is injected into a motorcycle dry-load storage battery with the model number of 3-MA10, and the unit cell voltage reaches 2.00-2.10V after 2-3 minutes; the voltage of the single lattice reaches 2.15-2.27 volts after charging for 3 hours and 15 minutes; the total voltage reaches 6.5-6.8 volts, and then slowly drops to 6.5 volts and keeps stable and unchanged; the continuous discharge current for 5 seconds is 4.5-5 amperes, and is close to the level of a common lead-acid storage battery; the discharge was carried out for 3-4 hours at 6 volts/2.6 amps.

According to the best embodiment of the invention, dilute sulfuric acid with specific gravity of 1.40, plaster and alkyd varnish are prepared into paste colloid electrolyte according to the volume ratio of 2.5: 1.0: 0.4, the paste colloid electrolyte is injected into a motorcycle dry storage battery with the model number of 3-MA-10, the unit cell voltage after 2-3 minutes is 2.05 volts, and the total voltage is 6.16 volts; after charging for 3 hours and 15 minutes, the total voltage rises to 6.7 volts, and then slowly drops to 6.5 volts and keeps stable; the continuous discharge current for 5 seconds is 4.6 amperes, and is more than 90% of the same capacity of a lead-acid storage battery, but is larger than that of a colloid storage battery (80%). The discharge current level of a typical lead-acid battery can be achieved if the specific gravity density of the electrolyte is slightly increased during the electrolyte preparation.

Since plaster of Paris and alkyd varnish are added in addition to dilute sulfuric acid to the electrolyte of the lead-acid battery of the invention, the electrolyte in the battery of the invention is in the form of a paste colloid. Because the fluidity of the paste colloid is much lower than that of the common dilute sulfuric acid, the electrolyte can not splash out of the storage battery to hurt human bodies or other nearby machines, which is one of the most outstanding advantages of the invention. The paste colloid accumulator is not afraid of inclination and jolt in use, and is especially suitable for use in automobile, ship, airplane and naval vessel. The paste colloid accumulator of the present invention has longer service time than common lead-acid accumulator with the same capacity because the electrolyte will not be splashed out during use.

As is well known, ordinary leadThe electrolyte of the acid storage battery has small specific weight (1.28-1.30), so the capacity is large, but the electrolyte is easy to splash; the electrolyte of the common colloid accumulator has large specific gravity (1.48-1.50), and solves the problem of splashing, but has large specific gravity, high viscosity and large internal resistance, so the capacity is small, and is only 80% of that of the same lead-acid accumulator. The specific weight of electrolyte in the pasty colloid lead-acid accumulator (1.40) is between the specific weight of the electrolyte in the above two accumulators, thus ensuring no splashing and not losing the capacity of the accumulator too much. If plaster of paris (b) is taken into account

) The specific gravity of the electrolyte in the storage battery of the invention is only about 1.35 actually due to the effect of the middle water. Therefore, the capacity characteristics of the accumulator of the invention are necessarily superior to those of colloid accumulator and are close to commonLead-acid accumulator.

It was found by experimentation that the alkyd varnish formed a very thin, uniform film on both the plates and on the separator. The films protect the polar plates and the separators and can prevent the active substances from falling off from the polar plates, thereby prolonging the service life of the storage battery, and the films can ensure that the contact between the electrolyte and the polar plates is more uniform than that ofa colloid storage battery, so that the occurrence of self-discharge can be reduced. In fact, the generation of a film is inevitable because the specific gravity of alkyd varnish is lower than that of sulfuric acid, distilled water and plaster of paris.

Furthermore, it has been found through experimentation that the batteries of the present invention normally charge for 1-2 hours, or even more, less than conventional lead-acid batteries.

The performance of the accumulator of the invention is superior to that of the common accumulator. Except for dilute sulfuric acid, the used plaster of paris and alkyd varnish are not much. Four 3-MA-14 storage batteries of the motorcycle can be prepared by 1 kg of plaster of paris and thirty storage batteries can be prepared by 1 kg of alkyd varnish. Therefore, the storage battery of the invention has low cost, simple production method and convenient batch production.

Claims

1. A paste-like lead-acid battery comprising:

a positive electrode plate group consisting of a plurality of positive electrode plates filled with an active material pbo₂The positive plates are connected by a transverse plate with an electric pile;

a negative electrode plate group consisting of a plurality of negative electrode plates filled with an active material pb and connected by another cross plate with another electric pile, and each of said negative electrode plates being fitted to each of said positive electrode plates of said positive electrode plate group at intervals;

a plurality of separators made of a porous insulating material and inserted between the positive and negative electrode plates;

a housing container for housing said positive and negative electrode plate sets, said separator and electrolyte;

the accumulator also includes electrolyte filled into the container, the electrolyte includes dilute sulfuric acid with specific gravity of 1.40, plaster and alkyd varnish, the volume ratio of the three is:

(2-3)∶(0.7-1.5)∶(0.3-0.8)。

2. a pasted colloidal lead-acid storage battery according to claim 1, wherein said electrolyte contains dilute sulfuric acid having a specific gravity of 1.40, thermal gypsum and alkyd varnish in the following order by volume:

2.5∶1.0∶0.4。

3. a method for manufacturing a pasted colloidal lead-acid battery as defined in claim 1, said battery comprising a positive electrode plate group, a negative electrode plate group, a plurality of separators, a can container, characterized in that the method comprises the steps of, in order:

(a) diluting sulfuric acid with distilled water to specific gravity of 1.40, and taking 2-3 parts (by volume) of diluted sulfuric acid with specific gravity of 1.40; then slowly pouring 0.7-1.5 parts by volume of hot gypsum into the dilute sulfuric acid, and slightly stirring by using a glass rod or a wood stick to gradually reduce the foam on the surface of the hot gypsum to form blocks; then, slowly pouring 0.3-0.8 part of alkyd varnish into the mixed solution of the dilute sulfuric acid and the hot gypsum, and quickly stirring until the alkyd varnish is in a porridge shape;

(b) injecting said prepared electrolyte into said housing container containing said positive electrode plate group, said negative electrode plate group, and said separator;

(c) cooling said housing container filled with said electrolyte to below 15 ℃;

(d) initial charging: charging with 1/10 rated current for 1-3 hr, adding reduced electrolyte, charging with 1/20 rated current for 40 min, and finishing the initial charging step.

4. A method for manufacturing a pasted colloidal lead-acid storage battery as claimed in claim 3, wherein said dilute sulfuric acid having a specific gravity of 1.40, plaster of paris and alkyd varnish in step (a) are in the following order by volume ratio:

2.5∶1.0∶0.4。