CN1960049A - Activity increase agent for lead-acid storage battery - Google Patents
Activity increase agent for lead-acid storage battery Download PDFInfo
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- CN1960049A CN1960049A CNA200610123620XA CN200610123620A CN1960049A CN 1960049 A CN1960049 A CN 1960049A CN A200610123620X A CNA200610123620X A CN A200610123620XA CN 200610123620 A CN200610123620 A CN 200610123620A CN 1960049 A CN1960049 A CN 1960049A
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Abstract
The disclosed activator for lead-acid accumulator includes distilled water, sulfuric acid, cobalt sulfate, hydroxylamine sulfate, aluminum sulfate, cadmium sulfate, magnesium sulfate, and binary carboxylic acid. Advantages are: preventing pole plates from vulcanizing, increasing capacity and service life of accumulator, shortening time for charging accumulator, reducing evaporation of electrolyte in use, reducing internal resistance, avoiding overcharge. Moreover, the invention solves self-discharge issue of accumulator effectively.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to an activator for a lead-acid storage battery.
Background
China is a big country for producing and using storage batteries. The battery is widely applied to the fields of mechanical power, firepower, water power, solar energy, wind power generation and the like, and can also provide electric energy for automobiles, trains, airplanes, steamships, naval vessels, tanks, armored vehicles, battery cars, electric bicycles and the like. It goes deep into various fields of national economic construction, national defense construction and daily life. However, the existing storage battery has many defects. (1) Easy vulcanization: the battery polar plate is easy to vulcanize, so that the polar plate is damaged, and the battery is scrapped too early; 75% of the damaged and scrapped storage batteries are caused by vulcanization. (2) Only 75-80% of active substances of the new battery cell play a role, and a part of the new battery cell does not play a role, so that the battery cell can not be used any more when being scrapped. (3) Short service life: the existing storage battery can be used for only 8 months generally, and can be used for only 3 months in some cases. (4) The charging time is long: in a common battery, about 70 hours is needed for one-time charging. (5) Poor cold resistance: under the condition of-20 ℃, the storage battery is not easy to start. (6) Poor heat resistance: the electrolyte in the storage battery is easy to evaporate, and water needs to be added frequently.
The invention patent publication discloses a lead-acid battery capacity-increasing liquid (patent No. 93103819.7), which comprises distilled water, sulfuric acid, cobalt sulfate, hydroxylamine sulfate, aluminum sulfate, cadmium sulfate and magnesium sulfate. Although it improves the performance of lead acid batteries, there is still room for further improvement.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides the lead-acid battery activator which ensures that a battery is not easy to vulcanize, has high capacity, long service life, short charging time and good cold resistance and heat resistance.
In order to solve the technical problem, the method is realized by the following technical scheme:
the lead-acid battery activator comprises distilled water, sulfuric acid, cobalt sulfate, hydroxylamine sulfate, aluminum sulfate, cadmium sulfate, magnesium sulfate and dicarboxylic acid. The composition ratio is as follows
Raw material number name specification amount: parts by weight
1 distilled water deionized water 125-
2 sulfuric acid more than or equal to 98 percent and 50 to 54 percent
3 analytically pure cobalt sulfate 1.4-1.8
4 hydroxylamine sulfate analytically pure 1-1.3
5-9 analytically pure aluminum sulfate
6 cadmium sulfate analytically pure 4-6
7 analytically pure magnesium sulfate 2.7-3.7
8 dicarboxylic acid analytically pure 3-5
The lead-acid battery activator also comprises citric acid. The components of the activator for lead-acid storage battery are as follows
Raw material number name specification amount: parts by weight
1 distilled water deionized water 125-
2 sulfuric acid more than or equal to 98 percent and 50 to 54 percent
3 analytically pure cobalt sulfate 1.4-1.8
4 hydroxylamine sulfate analytically pure 1-1.3
5-9 analytically pure aluminum sulfate
6 cadmium sulfate analytically pure 4-6
7 analytically pure magnesium sulfate 2.7-3.7
8 dicarboxylic acid analytically pure 3-5
9 citric acid analytically pure 3-5
The dicarboxylic acid is one or any combination of oxalic acid, malonic acid and succinic acid.
Adding the No. 2 raw material into the No. 1 raw material under continuous stirring according to the sequence; after dissolving, adding the No. 3 raw material into the mixed solution of the No. 1 raw material and the No. 2 raw material; after dissolving, adding the No. 4 raw material into the mixed solution of the No. 1, the No. 2 and the No. 3 raw materials; after dissolving, adding the No. 5 raw material into the mixed solution of the No. 1, No. 2, No. 3 and No. 4 raw materials; after dissolving, adding the No. 6 raw material into the mixed solution of the No. 1, No. 2, No. 3, No. 4 and No. 5 raw materials; adding the No. 7 raw material into the mixed solution of the No. 1, No. 2, No. 3, No. 4, No. 5 and No. 6 raw materials; adding the No. 8 raw material into the mixed solution of the No. 1, No. 2, No. 3, No. 4, No. 5, No. 6 and No. 7 raw materials, and mixing to obtain the mixed solution, namely the lead-acid battery activator.
In addition, the No. 9 raw material can be added into the mixed liquid of the No. 1, No. 2, No. 3, No. 4, No. 5, No. 6, No. 7 and No. 8 raw materials, and the mixed liquid obtained after mixing is the lead-acid battery activator with better effect.
The principle of the invention for eliminating and preventing the vulcanization of the battery is described below.
The lead-acid battery is a reversible electrochemical reaction, can realize repeated charge and discharge, and has an electrochemical reaction equation as follows:
wherein, PbO2Located at the positive plate and Pb at the negative plate.
When the storage battery is in a discharging or semi-discharging state due to improper maintenance or long-term storage, a white, coarse and hard lead sulfate crystal (PbSO) is generated on the polar plate4) The crystal has extremely poor conductivity and is difficult to dissolve, and can block the capillary pores of the active substance, hinder the convection and diffusion of the electrolyte, increase the internal resistance of the battery, destroy the normal electrochemical reaction and cause the capacity reduction. If the current is increased and the charging is hard, the polar plate will be loosenedThe battery is damaged and discarded.
After the lead-acid battery activator is added into a vulcanized battery, electrochemical reaction is generated inside the battery, so that sulfide is softened, refined and dissolved in electrolyte, reversible electrochemical reaction inside the battery is increased, and white hard lead sulfate crystals (PbSO) are obtained4) Lead dioxide (PbO) converted into sponge shape after charging and recovery2) Army lead (Pb) to restore the function of the failed battery, thereby achieving the purpose of prolonging the servicelife of the battery. After the lead-acid battery activator is added into an unvulcanized battery, a protective film is formed around a polar plate of the battery, so that the polar plate is prevented from being vulcanized, the conductivity and the charging efficiency of electrolyte are improved, the internal resistance is reduced, the evaporation of the electrolyte is reduced, the maintenance effect is generated, and the service life of the battery is effectively prolonged.
The concrete description is as follows: the sign of the battery discharge end is that the specific gravity of the electrolyte is reduced to 1.10, and the voltage of the battery is reduced to 1.05V. The end of charge is marked by a voltage rise to 2.2 volts and an electrolyte specific gravity rise to 1.28. The specific gravity of the electrolyte of a common storage battery is increased to about 1.28, and a large amount of bubbles appear in the electrolyte and are in a boiling state. When the storage battery is in a discharge or semi-discharge state for a long time, a white coarse crystal is formed on a polar plate, the white coarse crystal cannot be converted into lead dioxide and johns-shaped lead during normal charge, the lead sulfate is hardened or vulcanized, the capacity of the storage battery is obviously reduced, and the cell voltage is obviously reduced. During charging, the cell voltage rapidly rises to about 2.8V, the specific gravity of the electrolyte does not rise obviously, and the boiling phenomenon occurs. This is because white and hard crystal grains block the gap of the electrode plate, and the action surface of the electrode plate and the electrolyte is reduced, so that the capacity is reduced, the internal resistance is increased, and the starting is difficult. The battery pole plate with serious pole plate vulcanization expands to promote the sulfide to fill in the gap of the clapboard, so that the current flow is blocked, the discharge is not uniform, and even the pole plate is bent and the like.
In the discharge process of the storage battery, active substances in the storage battery are mainly in combination and decomposition motion. During discharging, sulfuric acid is reduced, water is increased, and the specific gravity of the electrolyte is reduced; the opposite is true during charging. When the charging of the battery is finished, only 30-35% of active substances are actually converted into lead sulfate, and 65-70% of active substances on the polar plate are not changed. In order to improve the power supply capacity, the dicarboxylic acid and the citric acid are added on the basis of the prior art, impurities in the electrolyte are purified, the vulcanization and the internal self-discharge of the storage battery are effectively prevented, the capacity of the storage battery is increased, and the effect of prolonging the service life of the storage battery is achieved.
Compared with the prior art, the lead-acid battery activating agent disclosed by the invention is added into a battery, and has the following beneficial effects: (1) the sulfuration of a polar plate of the storage battery is prevented, the capacity of the storage battery is improved, the capacity of a new storage battery is 100 percent, and the capacity of an old storage battery is 85 percent; (2) the service life of the storage battery is prolonged and can be generally prolonged by 2 times of the original service life of the storage battery; (3) the invention also shortens the charging time of the storage battery, only needs half of the original charging time, even 1/3, reduces the evaporation of the electrolyte in use, reduces the internal resistance of the storage battery and prevents overcharge; (4) the cold resistance and heat resistance of the battery are high, and the internal temperature can still be normally started at +/-40 ℃; (5) the invention effectively solves the problem of self-discharge of the storage battery, and the charged storage battery can still be used after being placed statically for 8 months; (6) the evaporation of water in the storage battery is reduced, the normal use of the storage battery can be ensured only by adding water into the storage battery for 1-2 times every year, and the maintenance-free storage battery can be free of adding water; (7) the electrochemical reaction speed is improved, the internal resistance of the storage battery is reduced, and the output power is improved; (8) the recovery and self-regeneration capacity of the storage battery is enhanced, and the large-current continuous service performance of the storage battery is improved; (9) the invention can regenerate and revive the storage battery which is vulcanized seriously but has a good and continuous internal mechanical structure; (10) the storage battery with serious electric leakage recovers the normal function after being added with the invention, and can reduce the electric leakage phenomenon when the storage battery is not used at rest.
The invention can generate huge social effect and economic effect at the same time. As is well known, lead-acid batteries have good safety and low price, and once the problems of service life, charging time and the like are solved, the lead-acid batteries can be more widely used. According to statistics, the quantity of automobiles in China reaches 5000 thousands by 6 months in 2006, and if all lead-acid storage batteries on the automobiles are provided with the activating agent, about billions of capital can be saved for the nation every year. Particularly for the environment-friendly electric automobile concerned all over the world, if the lead-acid battery of the activating agent is used, the problem of large-scale production of the electric automobile can be solved. In addition, the price of the lead-acid battery is 1/7 of the price of a lithium battery and a nickel-hydrogen battery.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example one
125 kg of distilled water is added into a 300 cubic meter enamel reaction kettle with a stirrer, 50 kg of sulfuric acid is slowly added under continuous stirring, the temperature is increased, and when the temperature is reduced to 25-30 ℃, 1.4 kg of cobalt sulfate, 1 kg of hydroxylamine sulfate, 5 kg of aluminum sulfate, 4 kg of cadmium sulfate, 2.7 kg of magnesium sulfate and 3 kg of oxalic acid are sequentially added. In the process of adding the raw materials, the former raw material is required to be dissolved, and then the latter raw material is added.
Example two
The equipment and the steps of the embodiment are the same as those of the embodiment I, and the raw materials comprise 135 kg of distilled water, 54 kg of sulfuric acid, 1.8 kg of cobalt sulfate, 1.3 kg of hydroxylamine sulfate, 9 kg of aluminum sulfate, 6 kg of cadmium sulfate, 3.7 kg of magnesium sulfate and 5 kg of oxalic acid.
EXAMPLE III
The equipment and procedure of this example are the same as in example one, and the raw materials include distilled water 130 kg, sulfuric acid 52 kg, cobalt sulfate 1.6 kg, hydroxylamine sulfate 1.2 kg, aluminum sulfate 7 kg, cadmium sulfate 5 kg, magnesium sulfate 3.1 kg, and oxalic acid 4 kg.
Example four
The equipment and the steps of the embodiment are the same as those of the first embodiment, and the raw materials comprise 130 kg of distilled water, 52 kg of sulfuric acid, 1.6 kg of cobalt sulfate, 1.2 kg of hydroxylamine sulfate, 7 kg of aluminum sulfate, 5 kg of cadmium sulfate, 3.1 kg of magnesium sulfate and 4 kg of malonic acid.
EXAMPLE five
The equipment and the steps of the embodiment are the same as those of the first embodiment, and the raw materials comprise 130 kg of distilled water, 52 kg of sulfuric acid, 1.6 kg of cobalt sulfate, 1.2 kg of hydroxylamine sulfate, 7 kg of aluminum sulfate, 5 kg of cadmium sulfate, 3.1 kg of magnesium sulfate and 4 kg of succinic acid.
EXAMPLE six
The equipment and procedure of this example are the same as in example one, and the raw materials include 128 kg of distilled water, 51 kg of sulfuric acid, 1.5 kg of cobalt sulfate, 1.1 kg of hydroxylamine sulfate, 6 kg of aluminum sulfate, 4.8 kg of cadmium sulfate, 3 kg of magnesium sulfate, 3.5 kg of oxalic acid, and 4.5 kg of citric acid.
EXAMPLE seven
The apparatus and procedure of this example were the same as in example one, and the raw materials were 128 kg of distilled water, 51 kg of sulfuric acid, 1.5 kg of cobalt sulfate, 1.1 kg of hydroxylamine sulfate, 6 kg of aluminum sulfate, 4.8 kg of cadmium sulfate, 3 kg of magnesium sulfate, 3.5 kg of malonic acid, and 4.5 kg of citric acid.
Example eight
The equipment and the steps of the embodiment are the same as those of the embodiment one, and the raw materials comprise 132 kg of distilled water, 53 kg of sulfuric acid, 1.7 kg of cobalt sulfate, 1.15 kg of hydroxylamine sulfate, 8 kg of aluminum sulfate, 5.2 kg of cadmium sulfate, 3.6 kg of magnesium sulfate, 4.5 kg of succinic acid and 3.7 kg of citric acid.
Example nine
The apparatus and procedure of this example are the same as in example one, and the raw materials include 135 kg of distilled water, 54 kg of sulfuric acid, 1.8kg of cobalt sulfate, 1.3 kg of hydroxylamine sulfate, 9 kg of aluminum sulfate, 6 kg of cadmium sulfate, 3.7 kg of magnesium sulfate, 4 kg of a combination of oxalic acid and malonic acid (2 kg of oxalic acid and 2 kg of malonic acid), and 5 kg of citric acid.
Example ten
The apparatus and procedure of this example are the same as in example one, and the raw materials include distilled water 125 kg, sulfuric acid 50 kg, cobalt sulfate 1.4 kg, hydroxylamine sulfate 1 kg, aluminum sulfate 5 kg, cadmium sulfate 4 kg, magnesium sulfate 2.7 kg, succinic acid and malonic acid composition 5 kg (succinic acid 2.5 kg, malonic acid 2.5 kg), and citric acid 3 kg.
EXAMPLE eleven
The apparatus and procedure of this example are the same as in example one, and the raw materials include distilled water 130 kg, sulfuric acid 52 kg, cobalt sulfate 1.6 kg, hydroxylamine sulfate 1.2 kg, aluminum sulfate 7 kg, cadmium sulfate 5 kg, magnesium sulfate 3.1 kg, oxalic acid and malonic acid and succinic acid composition 5 kg (wherein oxalic acid 2 kg, malonic acid 1.5 kg, succinic acid 1.5 kg), citric acid 4 kg.
Example twelve
The apparatus and procedure of this example are the same as in example one, and the raw materials include distilled water 130 kg, sulfuric acid 52 kg, cobalt sulfate 1.6 kg, hydroxylamine sulfate 1.2 kg, aluminum sulfate 7 kg, cadmium sulfate 5 kg, magnesium sulfate 3.1 kg, oxalic acid and malonic acid and succinic acid composition 5 kg (wherein oxalic acid 1 kg, malonic acid 1.5 kg, succinic acid 2.5 kg), citric acid 4 kg.
The above embodiments are only used to illustrate but not to limit the technical solutions of the present invention. For example, the order of mixing the raw materials may be adjusted, and the specific gravity of each raw material is not limited thereto. In addition, oxalic acid, malonic acid and succinic acid can be replaced by other dicarboxylic acids. Any modification or partial replacement without departing from the spirit and scope of the present invention should be covered in the claims of the present invention.
Claims (5)
1. The lead-acid battery activator comprises distilled water, sulfuric acid, cobalt sulfate, hydroxylamine sulfate, aluminum sulfate, cadmium sulfate, magnesium sulfate and is characterized by also comprising dicarboxylic acid.
2. The lead-acid battery activator according to claim 1, wherein the components are mixed in the following ratio
Raw material name, specification and dosage: parts by weight
Distilled water deionized water 125-135
50-54 percent of sulfuric acid with the concentration of more than or equal to 98 percent
Analytically pure cobalt sulfate 1.4-1.8
Hydroxylamine sulfate analytically pure 1-1.3
Analytical pure 5-9 of aluminum sulfate
Analytical purity of cadmium sulfate 4-6
Analytically pure magnesium sulfate 2.7-3.7
Dicarboxylic acid analytically pure 3-5
3. The lead-acid battery activator according to claim 1, further comprising citric acid.
4. The lead-acid battery activator according to claim 3, wherein the proportion of each component of the lead-acid battery activator is as follows
Raw material name, specification and dosage: parts by weight
Distilled water deionized water 125-135
50-54 percent of sulfuric acid with the concentration of more than or equal to 98 percent
Analytically pure cobalt sulfate 1.4-1.8
Hydroxylamine sulfate analytically pure 1-1.3
Analytical pure 5-9 of aluminum sulfate
Analytical purity of cadmium sulfate 4-6
Analytically pure magnesium sulfate 2.7-3.7
Dicarboxylic acid analytically pure 3-5
Citric acid analytically pure 3-5
5. The lead-acid battery activator according to claim 1, 2, 3 or 4, wherein the dicarboxylic acid is one of oxalic acid, malonic acid, succinic acid, or any combination thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200610123620XA CN100440604C (en) | 2006-11-17 | 2006-11-17 | Activity increase agent for lead-acid storage battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200610123620XA CN100440604C (en) | 2006-11-17 | 2006-11-17 | Activity increase agent for lead-acid storage battery |
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| CN1960049A true CN1960049A (en) | 2007-05-09 |
| CN100440604C CN100440604C (en) | 2008-12-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010049143A1 (en) * | 2008-10-28 | 2010-05-06 | Vb Autobatterie Gmbh & Co. Kgaa | Spreading means for the active material of a negative electrode |
| CN103682468A (en) * | 2013-12-04 | 2014-03-26 | 河南超威电源有限公司 | Electromobile lead acid storage battery electrolyte |
| CN106025360A (en) * | 2016-05-25 | 2016-10-12 | 江苏帕维电动科技有限公司 | Storage battery reinforcing agent and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05225999A (en) * | 1991-02-22 | 1993-09-03 | Tokai Sangyo Kk | Function restoration agent for lead-acid battery and function restoration method for lead-acid battery |
| CN1040926C (en) * | 1993-04-05 | 1998-11-25 | 刘笃清 | Capacity increasing liquid for lead-acid accumulators |
| DE19959289A1 (en) * | 1999-12-09 | 2001-06-13 | Axiva Gmbh | Process for the production of sulfonated aromatic polymers and use of the process products for the production of membranes |
-
2006
- 2006-11-17 CN CNB200610123620XA patent/CN100440604C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010049143A1 (en) * | 2008-10-28 | 2010-05-06 | Vb Autobatterie Gmbh & Co. Kgaa | Spreading means for the active material of a negative electrode |
| CN102203991A (en) * | 2008-10-28 | 2011-09-28 | Vb汽车电池有限责任公司 | Spreading means for the active material of a negative electrode |
| US8932755B2 (en) | 2008-10-28 | 2015-01-13 | Johnson Controls Autobatterie Gmbh & Co. Kgaa | Spreading means for the active material of a negative electrode |
| CN102203991B (en) * | 2008-10-28 | 2016-01-13 | 约翰逊控制汽车电池有限责任公司 | For the swelling agent of negative active core-shell material |
| CN103682468A (en) * | 2013-12-04 | 2014-03-26 | 河南超威电源有限公司 | Electromobile lead acid storage battery electrolyte |
| CN103682468B (en) * | 2013-12-04 | 2017-01-11 | 河南超威电源有限公司 | Electromobile lead acid storage battery electrolyte |
| CN106025360A (en) * | 2016-05-25 | 2016-10-12 | 江苏帕维电动科技有限公司 | Storage battery reinforcing agent and preparation method thereof |
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| CN100440604C (en) | 2008-12-03 |
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