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CN111009657A - Lead-antimony oxide and preparation method and application thereof - Google Patents

Lead-antimony oxide and preparation method and application thereof Download PDF

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Publication number
CN111009657A
CN111009657A CN201911223395.0A CN201911223395A CN111009657A CN 111009657 A CN111009657 A CN 111009657A CN 201911223395 A CN201911223395 A CN 201911223395A CN 111009657 A CN111009657 A CN 111009657A
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lead
powder
antimony oxide
oxide
antimony
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李志斌
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Guangzhou Edenta Chemical Co Ltd
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Guangzhou Edenta Chemical Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • H01M4/57Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a lead-antimony oxide and a preparation method and application thereof. The preparation method of the lead-antimony oxide comprises the following steps: uniformly mixing antimony oxide powder and lead oxide powder according to a molar ratio of 1: 0.5-3, placing the mixture in a high-temperature reaction container, heating to 500-700 ℃, reacting for 1-3 h, cooling, and grinding to obtain the lead-antimony oxide. The lead-antimony oxide provided by the invention has a high purity, and the lead-antimony oxide added in the lead plaster formula can weaken the defect of early capacity attenuation of the battery and can not inhibit the generation of a 4BS crystal structure of the lead plaster, so that the lead-antimony oxide has a 3BS crystal structure compared with the structure of the lead plaster with antimony trioxide added in the lead plaster, and has great significance for prolonging the cycle life of the lead-acid battery.

Description

Lead-antimony oxide and preparation method and application thereof
Technical Field
The invention relates to the technical field of inorganic chemistry, in particular to a lead-antimony oxide and a preparation method and application thereof.
Background
The lead plaster is a matrix of an active substance of a polar plate, is a pasty substance with certain plasticity formed by mechanically stirring and mixing lead powder with certain oxidation degree and apparent density, water and sulfuric acid, and has the function of providing and storing the required substances for electrochemical reaction in the lead-acid battery. The positive electrode lead paste of lead acid batteries generally has two structures: one is 3BS structure, tribasic lead sulfate; the other one is 4BS structure and tetrabasic lead sulfate, wherein the lead plaster of the 3BS structure is in a sand-shaped appearance, and the cycle life of the battery made of the lead plaster is short; the lead plaster with the 4BS structure is in a stone-shaped appearance, and the cycle life of the battery is prolonged. In general, the 3BS crystal structure is easy to generate under the condition of low temperature (not higher than 55 ℃); while at high temperatures (above 55 degrees) the 4BS crystal structure is favored.
The lead-calcium alloy grid system is used for the grid, and the antimony element is an essential element of the lead plaster in the lead-calcium alloy grid system. In order to avoid early capacity fading of the storage battery, antimony trioxide is usually added into a lead paste formula to improve the conductivity of a grid corrosion interface and improve the bonding force between the grid and the lead paste. However, the addition of antimony trioxide can cause that the lead paste cannot form a 4BS structure in the preparation process, and the 4BS structure cannot be formed despite high-temperature curing. It is therefore desirable to provide an antimony-containing compound that retains its original effectiveness in overcoming the early capacity fade of the battery, but does not inhibit the formation of the 4BS crystal structure of the lead paste.
Disclosure of Invention
The invention aims to provide a lead-antimony oxide, a preparation method and application thereof, so as to solve the technical problems.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect, the present invention provides a method for preparing lead antimony oxide, comprising the following steps:
uniformly mixing antimony oxide powder and lead oxide powder according to a molar ratio of 1: 0.5-3, placing the mixture in a high-temperature reaction container, heating to 500-700 ℃, reacting for 1-3 h, cooling, and grinding to obtain the lead-antimony oxide.
Preferably, the antimony oxide is antimony trioxide.
Preferably, the lead oxide is at least one of lead oxide, lead tetroxide, lead dioxide and lead trioxide.
Preferably, the chemical formula of the lead antimony oxide is Sb2PbxOyWherein x and y are integers, x is more than or equal to 0 and less than or equal to 4, and y is more than or equal to 3 and less than or equal to 11.
Preferably, the chemical formula of the lead antimony oxide is Sb2PbxOyWherein x and y are integers, x is more than or equal to 1 and less than or equal to 4, and y is more than or equal to 5 and less than or equal to 11.
Preferably, the lead antimony oxide is selected from Sb2PbO5、Sb2Pb2O5、Sb2Pb2O6、Sb2Pb2O7、Sb2Pb3O6、Sb2Pb3O7、Sb2Pb3O8、Sb2Pb3O9、Sb2Pb4O7、Sb2Pb4O8、Sb2Pb4O9、Sb2Pb4O10、Sb2Pb4O11At least one of (1).
Preferably, the average particle size of the lead antimony oxide is 1 to 20 μm, and more preferably 3 to 8 μm.
Preferably, the purity of the lead antimony oxide is not less than 90%.
In a second aspect, the invention provides a lead-antimony oxide prepared by the method for preparing the lead-antimony oxide according to the first aspect.
In a third aspect, the invention provides a use of the lead antimony oxide as described in the second aspect in a battery positive electrode lead paste.
Compared with the prior art, the invention has the beneficial effects that:
the lead-antimony oxide provided by the invention has a simple preparation method, is suitable for industrial production, has high purity, can weaken the defect of early capacity attenuation of a battery by adding the lead-antimony oxide into a lead paste formula, does not inhibit the generation of a 4BS crystal structure of the lead paste, and has great significance for prolonging the cycle life of the lead-acid battery.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
Drying antimony trioxide powder and lead oxide powder, uniformly mixing the antimony trioxide powder and the lead oxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain a final product.
Example 2
Drying antimony trioxide powder and lead oxide powder, uniformly mixing the antimony trioxide powder and the lead oxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 550 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 3
Drying antimony trioxide powder and lead oxide powder, uniformly mixing the antimony trioxide powder and the lead oxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 600 ℃, reacting for 2 hours, cooling, and grinding to obtain a final product.
Example 4
Drying antimony trioxide powder and lead oxide powder, uniformly mixing the antimony trioxide powder and the lead oxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 650 ℃, reacting for 2 hours, cooling, and grinding to obtain a final product.
Example 5
Drying antimony trioxide powder and lead oxide powder, uniformly mixing the antimony trioxide powder and the lead oxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 700 ℃, reacting for 2 hours, cooling, and grinding to obtain a final product.
Example 6
Drying antimony trioxide powder and lead oxide powder, uniformly mixing the antimony trioxide powder and the lead oxide powder according to a molar ratio of 1:1, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain a final product.
Example 7
Drying antimony trioxide powder and lead oxide powder, uniformly mixing the antimony trioxide powder and the lead oxide powder according to a molar ratio of 1:3, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain a final product.
The components of the final products obtained in examples 1 to 7 were measured, and the measurement results are shown in table 1 below.
TABLE 1
Figure BDA0002301480170000031
Figure BDA0002301480170000041
Example 10
Drying antimony trioxide powder and lead dioxide powder, uniformly mixing the antimony trioxide powder and the lead dioxide powder according to the molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 1h, cooling, and grinding to obtain the final product.
Example 11
Drying antimony trioxide powder and lead dioxide powder, uniformly mixing the antimony trioxide powder and the lead dioxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 550 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 12
Drying antimony trioxide powder and lead dioxide powder, uniformly mixing the antimony trioxide powder and the lead dioxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 600 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 13
Drying antimony trioxide powder and lead dioxide powder, uniformly mixing the antimony trioxide powder and the lead dioxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 650 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 14
Drying antimony trioxide powder and lead dioxide powder, uniformly mixing the antimony trioxide powder and the lead dioxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 700 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 15
Drying antimony trioxide powder and lead dioxide powder, uniformly mixing the antimony trioxide powder and the lead dioxide powder according to a molar ratio of 1:1, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 16
Drying antimony trioxide powder and lead dioxide powder, uniformly mixing the antimony trioxide powder and the lead dioxide powder according to a molar ratio of 1:3, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
The components of the final products obtained in examples 10 to 16 were measured, and the measurement results are shown in table 2 below.
TABLE 2
Figure BDA0002301480170000051
Example 17
Drying antimony trioxide powder and lead tetroxide powder, uniformly mixing the antimony trioxide powder and the lead tetroxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 18
Drying antimony trioxide powder and lead tetroxide powder, uniformly mixing the antimony trioxide powder and the lead tetroxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction vessel, heating to 550 ℃, reacting for 1h, cooling, and grinding to obtain the final product.
Example 19
Drying antimony trioxide powder and lead tetroxide powder, uniformly mixing the antimony trioxide powder and the lead tetroxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction vessel, heating to 600 ℃, reacting for 1h, cooling, and grinding to obtain the final product.
Example 20
Drying antimony trioxide powder and lead tetroxide powder, uniformly mixing the antimony trioxide powder and the lead tetroxide powder according to a molar ratio of 1:1, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
The components of the final products obtained in examples 17 to 20 were measured, and the measurement results are shown in table 3 below.
TABLE 3
Figure BDA0002301480170000061
Example 21
Drying antimony trioxide powder and lead trioxide powder, uniformly mixing the antimony trioxide powder and the lead trioxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 22
Drying antimony trioxide powder and lead trioxide powder, uniformly mixing the antimony trioxide powder and the lead trioxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 550 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 23
Drying antimony trioxide powder and lead trioxide powder, uniformly mixing the antimony trioxide powder and the lead trioxide powder according to a molar ratio of 1:2, placing the mixture in a high-temperature reaction container, heating to 600 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
Example 24
Drying antimony trioxide powder and lead trioxide powder, uniformly mixing the antimony trioxide powder and the lead trioxide powder according to a molar ratio of 1:1, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 1h, cooling, and grinding to obtain a final product.
The components of the final products obtained in examples 21 to 24 were measured, and the measurement results are shown in table 4 below.
TABLE 4
Figure BDA0002301480170000071
Effect example 1
In order to further illustrate the beneficial effects of the present invention, the lead antimony oxides obtained in the above examples 1, 10, 17 and 21 are respectively added into a lead paste formula, the amount of the lead antimony oxide added is 0.1% of the weight of the lead powder, and the other raw materials in the lead paste formula comprise: 1000Kg of lead powder, 1.2Kg of short fibers, 100Kg of pure water and 96Kg of sulfuric acid solution (mass concentration of 1.4g/mL) were used to prepare a lead plaster by the following method: adding lead powder, short fibers and lead-antimony oxide into a paste mixer, and stirring and mixing for 1-5 min to obtain a dry mixture; adding pure water into the obtained dry mixture, and stirring and mixing for 1-5 min to obtain a wet mixed material; and adding a sulfuric acid solution into the obtained wet mixed material, heating to 65 ℃, keeping the temperature, stirring for 15min, cooling to 45 ℃, continuously stirring for 10min, and adjusting the apparent specific gravity of the lead paste to obtain the battery anode lead paste. The obtained battery positive electrode lead paste has a 4BS structure (namely tetrabasic lead sulfate), which shows that the lead-antimony oxide obtained by the invention does not influence the generation of the 4BS lead paste structure.
Example 25
Uniformly mixing antimony trioxide and PbO powder according to the molar ratio of 1:3, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain Sb2Pb3O6Powder of Sb2Pb3O6Sb in powder2Pb3O6Has a purity of more than 90% and an average particle diameter of 8 μm.
Example 26
Antimony trioxide and PbO2Uniformly mixing the powder according to the molar ratio of 1:2:1, placing the powder in a high-temperature reaction container, heating to 670 ℃ and reacting2h, cooling, and grinding to obtain Sb2Pb3O7Powder of Sb2Pb3O7Sb in powder2Pb3O7Has a purity of more than 90% and an average particle diameter of 8 μm.
Example 27
Antimony trioxide and PbO2Uniformly mixing the powder according to the molar ratio of 1:1:2, placing the powder in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain Sb2Pb3O8Powder of Sb2Pb3O8Sb in powder2Pb3O8Has a purity of more than 90% and an average particle diameter of 5 μm.
Example 28
Antimony trioxide and PbO2Uniformly mixing the powder according to the molar ratio of 1:3, placing the powder in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain Sb2Pb3O9Powder of Sb2Pb3O9Sb in powder2Pb3O9Has a purity of more than 90% and an average particle diameter of 5 μm.
Example 29
Uniformly mixing antimony trioxide and PbO powder according to the molar ratio of 1:4, placing the mixture in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain Sb2Pb4O7Powder of Sb2Pb4O7Sb in powder2Pb4O7Has a purity of more than 90% and an average particle diameter of 8 μm.
Example 30
Antimony trioxide and PbO2Uniformly mixing the powder according to the molar ratio of 1:3:1, placing the powder in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain Sb2Pb4O8Powder of Sb2Pb4O8Sb in powder2Pb4O8Has a purity of more than 90% and an average particle diameter of 5 μm.
Example 31
Antimony trioxide and PbO2Uniformly mixing the powder according to the molar ratio of 1:2:2, placing the powder in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain Sb2Pb4O9Powder of Sb2Pb4O9Sb in powder2Pb4O9Has a purity of more than 90% and an average particle diameter of 5 μm.
Example 32
Antimony trioxide and PbO2Uniformly mixing the powder according to the molar ratio of 1:1:3, placing the powder in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain Sb2Pb4O10Powder of Sb2Pb4O10Sb in powder2Pb4O10Has a purity of more than 90% and an average particle diameter of 5 μm.
Example 33
Antimony trioxide and PbO2Uniformly mixing the powder according to the molar ratio of 1:4, placing the powder in a high-temperature reaction container, heating to 670 ℃, reacting for 2 hours, cooling, and grinding to obtain Sb2Pb4O11Powder of Sb2Pb4O11Sb in powder2Pb4O11Has a purity of more than 90% and an average particle diameter of 8 μm.
Effect example 2
In order to further illustrate the beneficial effects of the invention, according to the method of effect embodiment 1, the lead antimony oxides obtained in the above embodiments 25 to 33 are respectively added to a lead paste formula to finally obtain the battery positive electrode lead paste, and the obtained battery positive electrode lead pastes have 4BS structures (i.e. tetrabasic lead sulfate), which indicates that the lead antimony oxides obtained in the embodiments 25 to 33 do not affect the generation of the 4BS lead paste structures.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.

Claims (10)

1. The preparation method of the lead-antimony oxide is characterized by comprising the following steps of:
uniformly mixing antimony oxide powder and lead oxide powder according to a molar ratio of 1: 0.5-3, placing the mixture in a high-temperature reaction container, heating to 500-700 ℃, reacting for 1-10 h, cooling, and grinding to obtain the lead-antimony oxide.
2. The method according to claim 1, wherein said antimony oxide is antimony trioxide.
3. The method according to claim 1, wherein the lead oxide is at least one of lead oxide, lead tetraoxide, lead dioxide and lead sesquioxide.
4. The method according to claim 1, wherein the chemical formula of the Pb-Sb oxide is Sb2PbxOyWherein x and y are integers, x is more than or equal to 0 and less than or equal to 4, and y is more than or equal to 3 and less than or equal to 11.
5. The method according to claim 1, wherein the chemical formula of the Pb-Sb oxide is Sb2PbxOyWherein x and y are integers, x is more than or equal to 1 and less than or equal to 4, and y is more than or equal to 5 and less than or equal to 11.
6. The method of claim 1, wherein the Pb-Sb oxide is Sb2PbO5、Sb2Pb2O5、Sb2Pb2O6、Sb2Pb2O7、Sb2Pb3O6、Sb2Pb3O7、Sb2Pb3O8、Sb2Pb3O9、Sb2Pb4O7、Sb2Pb4O8、Sb2Pb4O9、Sb2Pb4O10、Sb2Pb4O11At least one of (1).
7. The method for preparing lead-antimony oxide according to claim 1, wherein the average particle size of the lead-antimony oxide is 1 to 20 μm.
8. The method for preparing lead antimony oxide as claimed in claim 1, wherein the purity of the lead antimony oxide is not less than 90%.
9. A lead-antimony oxide characterized by being produced by the method for producing a lead-antimony oxide according to any one of claims 1 to 8.
10. Use of the lead antimony oxide of claim 9 in battery positive electrode lead paste.
CN201911223395.0A 2019-12-03 2019-12-03 Lead-antimony oxide and preparation method and application thereof Pending CN111009657A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723182A (en) * 1971-10-27 1973-03-27 Esb Inc Lead acid storage battery wherein a positive plate comprises antimonydispersed throughout the active material
CN1728425A (en) * 2004-07-27 2006-02-01 沈阳大学师范学院 Lithium ion battery cathode material and preparation method thereof
CN109196688A (en) * 2016-04-27 2019-01-11 Rsr技术公司 Lead-based alloys and related methods and products

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723182A (en) * 1971-10-27 1973-03-27 Esb Inc Lead acid storage battery wherein a positive plate comprises antimonydispersed throughout the active material
CN1728425A (en) * 2004-07-27 2006-02-01 沈阳大学师范学院 Lithium ion battery cathode material and preparation method thereof
CN109196688A (en) * 2016-04-27 2019-01-11 Rsr技术公司 Lead-based alloys and related methods and products

Non-Patent Citations (1)

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Title
LAURA RABBACHIN: ""Naples yellow and Pb-Sn-Sb yellow characterization and evaluation of their stability through a multi-analytical approach"", 《UNIVERSITA CA’FOSCARI VENEZIA》 *

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Application publication date: 20200414