CN113745501A - Silicon-based lead-acid storage battery positive lead paste and preparation method thereof - Google Patents
Silicon-based lead-acid storage battery positive lead paste and preparation method thereof Download PDFInfo
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- CN113745501A CN113745501A CN202110907028.3A CN202110907028A CN113745501A CN 113745501 A CN113745501 A CN 113745501A CN 202110907028 A CN202110907028 A CN 202110907028A CN 113745501 A CN113745501 A CN 113745501A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The positive lead plaster of the silicon-based lead-acid storage battery comprises the following components in parts by weight: 70-85 parts of lead powder, 0.5-1.5 parts of tetrabasic lead sulfate crystal, 0.5-1.2 parts of short fiber, 0.1-0.3 part of graphene, 0.1-0.5 part of colloidal graphite, 0.01-0.05 part of cobalt sulfate, 0.01-0.05 part of stannous sulfate, 0.01-0.1 part of antimony pentoxide, 5-8 parts of sulfuric acid and 7-15 parts of deionized water. The invention relates to a positive lead plaster and a preparation method thereof, which aims at the problem of combination of a silicon plate and the lead plaster in a silicon-based bipolar lead-acid storage battery and effectively solves the problems of poor high-current discharge and poor capacity caused by the fact that the positive lead plaster can not be effectively combined on the silicon plate. The lead plaster for the silicon-based battery has a strong PbO2 skeleton structure and good conductive capability, can be tightly combined with a lead alloy coating on a silicon plate, and is not easy to fall off in a circulating process, so that the large-current discharge capability of the silicon-based lead-acid battery is improved, and the circulating life of the silicon-based lead-acid battery is prolonged.
Description
Technical Field
The invention belongs to the technical field of storage battery processing, and particularly relates to a silicon-based lead-acid storage battery anode lead plaster and a preparation method thereof.
Background
Silicon-based bipolar lead-acid batteries have been studied by a number of researchers from the 80 s of the 20 th century. The silicon-based bipolar lead storage battery still follows the charge-discharge reaction of the conventional lead storage battery in principle, and has the characteristics of low cost, good heavy-current discharge performance, high and low temperature resistance, high safety, easiness in recycling and the like of the lead storage battery. The silicon-based bipolar lead-acid storage battery breaks a current path that a conventional lead storage battery flows back to a negative plate grid, a lug and a negative busbar from lead plaster and is then connected with a positive busbar, the lug, a positive plate grid and the positive lead plaster, and the current path is shortened greatly by ingeniously utilizing the conductive characteristic of a silicon substrate to enable the current to directly pass through the silicon substrate from the negative lead plaster to be connected in series to the positive lead plaster. Therefore, the silicon-based bipolar lead storage battery has the advantages of lead-acid batteries, unique reduction of lead consumption, better heavy-current discharge, grid corrosion defects and longer cycle life.
However, after more than thirty years of research, industrialization is still not achieved. The reason is mainly focused on that the silicon substrate can not be effectively contacted with the lead plaster, so that the poor discharge of large current can easily occur in the circulating process, and the lead plaster is prematurely dropped to cause short circulating life.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a silicon-based lead-acid storage battery anode lead plaster and a preparation method thereof, and the specific technical scheme is as follows:
the positive lead plaster of the silicon-based lead-acid storage battery comprises the following components in parts by weight:
70-85 parts of lead powder, 0.5-1.5 parts of tetrabasic lead sulfate crystal, 0.5-1.2 parts of short fiber, 0.1-0.3 part of graphene, 0.1-0.5 part of colloidal graphite, 0.01-0.05 part of cobalt sulfate, 0.01-0.05 part of stannous sulfate, 0.01-0.1 part of antimony pentoxide, 5-8 parts of sulfuric acid and 7-15 parts of deionized water.
Further, the oxidation degree of the lead powder is 70-90%, and the particle size of the tetrabasic lead sulfate crystal is 1-10 μm.
Further, the short fiber comprises one of polyester fiber and polypropylene fiber, and the length of the short fiber is 1-4 mm.
Further, the particle size of the graphene is less than 2 μm; the particle size of the colloidal graphite is less than 10 mu m; the mass fraction of the sulfuric acid is 40-50%.
A preparation method of silicon-based lead-acid storage battery positive electrode lead paste comprises the following steps:
adding lead powder, tetrabasic lead sulfate crystals, short fibers, graphene, colloidal graphite, cobalt sulfate, stannous sulfate and antimony pentoxide into a paste mixing machine according to preset components, and stirring for dry mixing;
adding deionized water into the paste mixing machine, stirring, and wet mixing;
adding sulfuric acid into the paste mixer, stirring, and carrying out acid mixing;
and detecting the product after acid mixing and obtaining paste.
Further, the lead powder, tetrabasic lead sulfate crystals, short fibers, graphene, colloidal graphite, cobalt sulfate, stannous sulfate and antimony pentoxide comprise the following preset components in parts by weight:
70-85 parts of lead powder, 0.5-1.5 parts of tetrabasic lead sulfate crystal, 0.5-1.2 parts of short fiber, 0.1-0.3 part of graphene, 0.1-0.5 part of colloidal graphite, 0.01-0.05 part of cobalt sulfate, 0.01-0.05 part of stannous sulfate and 0.01-0.1 part of antimony pentoxide; the dry mixing time is 3-6 min.
Further, the deionized water accounts for 7-15 parts by weight, and the time for adding the deionized water is 1-3 min; the wet mixing time is 4-6 min.
Further, the sulfuric acid comprises 5-8 parts by weight of sulfuric acid, the time for adding the sulfuric acid is 5-10 min, and the acid mixing time is 6-12 min.
Further, the temperature of the dry mixing, the wet mixing and the acid mixing is 50-70 ℃.
Further, the detection comprises apparent density detection, and the apparent density of the lead plaster is 4.10-4.45 g/mL; the paste discharge temperature was 45 ℃.
The invention has the beneficial effects that: the positive lead plaster and the preparation method thereof of the invention aim at the problem of combination of a silicon plate and the lead plaster in a silicon-based bipolar lead-acid storage battery, and effectively solve the problems of poor large-current discharge and poor capacity caused by the fact that the positive lead plaster can not be effectively combined on the silicon plate;
the lead plaster for the silicon-based battery has a strong PbO2 skeleton structure and good conductive capability, can be tightly combined with a lead alloy coating on a silicon plate, and is not easy to fall off in a circulating process, so that the large-current discharge capability of the silicon-based lead-acid battery is improved, and the circulating life of the silicon-based lead-acid battery is prolonged.
Drawings
FIG. 1 shows a schematic structural diagram of a silicon plate prepared by the present invention;
FIG. 2 shows a schematic diagram of a silicon plate prepared by the present invention after scribing;
fig. 3 shows a line graph of a battery prepared from a silicon plate of the present invention after cycle testing.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The positive lead plaster of the silicon-based lead-acid storage battery comprises the following components in parts by weight: 70-85 parts of lead powder, 0.5-1.5 parts of tetrabasic lead sulfate crystal, 0.5-1.2 parts of short fiber, 0.1-0.3 part of graphene, 0.1-0.5 part of colloidal graphite, 0.01-0.05 part of cobalt sulfate, 0.01-0.05 part of stannous sulfate, 0.01-0.1 part of antimony pentoxide, 5-8 parts of sulfuric acid and 7-15 parts of deionized water.
As an improvement of the technical scheme, the oxidation degree of the lead powder is 70-90%, and the particle size of the tetrabasic lead sulfate crystal is 1-10 μm.
As an improvement of the technical scheme, the short fiber comprises one of polyester fiber and polypropylene fiber, and the length of the short fiber is 1-4 mm.
As an improvement of the above technical solution, the particle size of the graphene is less than 2 μm; the particle size of the colloidal graphite is less than 10 mu m; the mass fraction of the sulfuric acid is 40-50%.
A preparation method of silicon-based lead-acid storage battery positive lead plaster comprises the following steps:
the method comprises the following steps: adding lead powder, tetrabasic lead sulfate crystals, short fibers, graphene, colloidal graphite, cobalt sulfate, stannous sulfate and antimony pentoxide into a paste mixing machine according to preset components, and stirring for dry mixing;
specifically, the lead powder, tetrabasic lead sulfate crystals, short fibers, graphene, colloidal graphite, cobalt sulfate, stannous sulfate and antimony pentoxide comprise the following preset components in parts by weight:
70-85 parts of lead powder, 0.5-1.5 parts of tetrabasic lead sulfate crystal, 0.5-1.2 parts of short fiber, 0.1-0.3 part of graphene, 0.1-0.5 part of colloidal graphite, 0.01-0.05 part of cobalt sulfate, 0.01-0.05 part of stannous sulfate and 0.01-0.1 part of antimony pentoxide; the components are added into a paste mixer according to the above components, and are mixed and stirred for 3-6 min in a dry mode.
Step two: adding deionized water into the paste mixing machine, stirring, and wet mixing;
specifically, deionized water is added into the paste mixing machine according to 7-15 parts by weight of the components, and the time for adding the deionized water is 1-3 min; adding deionized water and stirring for 4-6 min;
step three: adding sulfuric acid into the paste mixer, stirring, and carrying out acid mixing;
specifically, 5-8 parts by weight of sulfuric acid is added into the paste mixing machine for 5-10 min, and the acid mixing time is 6-12 min;
step four: detecting the product after the acid mixing and obtaining paste;
specifically, the detection comprises apparent density detection, and the apparent density of the lead plaster is 4.10-4.45 g/mL; the paste discharge temperature was 45 ℃.
As an improvement of the technical scheme, the temperature of dry mixing, wet mixing and acid mixing is 50-70 ℃.
Example (b):
1. determining a formula of the positive lead plaster, wherein the formula of the positive lead plaster comprises the following components in parts by weight: 80 parts of lead powder, 0.6 part of 4BS (tetrabasic lead sulfate) seed crystal, 0.5 part of polyester fiber short fiber, 0.3 part of graphene, 0.3 part of colloidal graphite, 0.01 part of cobalt sulfate, 0.02 part of stannous sulfate, 0.05 part of antimony pentoxide, 8 parts of sulfuric acid and 9 parts of deionized water.
2. Preparing the anode lead plaster, and preparing the anode lead plaster,
2.1, adding lead powder, tetrabasic lead sulfate crystals, short fibers, graphene, colloidal graphite, cobalt sulfate, stannous sulfate and antimony pentoxide into a paste mixing machine according to the components, stirring, controlling the temperature of the paste mixing machine to be 60 ℃, and carrying out dry mixing for 6 min;
2.2, adding deionized water into the paste mixing machine within 2min, stirring, and wet mixing for 12 min;
2.3, adding sulfuric acid into the paste mixing machine within 10min, stirring, and carrying out acid mixing for 12 min;
and 2.4, detecting the apparent density of the product after acid mixing, and discharging paste at 45 ℃.
3. Preparing a positive plate;
3.1, coating the prepared lead plaster on the surface of a grid:
3.2, immersing the grid into sulfuric acid and fishing out;
3.3, conveying the fished grid into a drying kiln, and drying for 5min at 100 ℃;
3.4, controlling the temperature of the curing furnace at 50 ℃ and curing for 48 hours;
3.5, drying the cured grid for 24 hours at the temperature of 60 ℃.
And (3) testing:
the completed silicon-based plate is shown in fig. 1, and as can be seen from fig. 1, the lead paste is tightly adhered to the silicon plate without bubbling or peeling.
When the lead paste was scraped off with a knife, it was found that the lead paste in contact with the silicon plate was still merely stuck to the silicon plate and was difficult to scrape off, as shown in fig. 2.
And (3) assembling the manufactured positive silicon wafer with a partition plate, a negative silicon wafer, a battery shell and a battery frame, adding acid for charging, and then performing a cycle test. Compared with a large-current circulation test, the large-current circulation performance of the silicon-based bipolar battery using the anode lead paste formula is far superior to that of a common silicon-based lead-acid storage battery, as shown in fig. 3.
The invention has the beneficial effects that: the invention relates to a positive lead plaster and a preparation method thereof, which aims at the problem of combination of a silicon plate and the lead plaster in a silicon-based bipolar lead-acid storage battery and effectively solves the problems of poor high-current discharge and poor capacity caused by the fact that the positive lead plaster can not be effectively combined on the silicon plate. The lead plaster for the silicon-based battery has a strong PbO2 skeleton structure and good conductive capability, can be tightly combined with a lead alloy coating on a silicon plate, and is not easy to fall off in a circulating process, so that the large-current discharge capability of the silicon-based lead-acid battery is improved, and the circulating life of the silicon-based lead-acid battery is prolonged.
It is noted that, in this document, relational terms such as first and second, and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The silicon-based lead-acid storage battery positive lead paste is characterized in that: the positive lead plaster formula comprises the following components in parts by weight:
70-85 parts of lead powder, 0.5-1.5 parts of tetrabasic lead sulfate crystal, 0.5-1.2 parts of short fiber, 0.1-0.3 part of graphene, 0.1-0.5 part of colloidal graphite, 0.01-0.05 part of cobalt sulfate, 0.01-0.05 part of stannous sulfate, 0.01-0.1 part of antimony pentoxide, 5-8 parts of sulfuric acid and 7-15 parts of deionized water.
2. The silicon-based lead-acid battery positive electrode lead paste according to claim 1, characterized in that: the oxidation degree of the lead powder is 70-90%, and the particle size of the tetrabasic lead sulfate crystal is 1-10 mu m.
3. The silicon-based lead-acid battery positive electrode lead paste according to claim 1, characterized in that: the short fiber comprises one of polyester fiber and polypropylene fiber, and the length of the short fiber is 1-4 mm.
4. The silicon-based lead-acid battery positive electrode lead paste according to claim 1, characterized in that: the particle size of the graphene is less than 2 mu m; the particle size of the colloidal graphite is less than 10 mu m; the mass fraction of the sulfuric acid is 40-50%.
5. A preparation method of silicon-based lead-acid storage battery positive lead plaster is characterized by comprising the following steps: the method comprises the following steps:
adding lead powder, tetrabasic lead sulfate crystals, short fibers, graphene, colloidal graphite, cobalt sulfate, stannous sulfate and antimony pentoxide into a paste mixing machine according to preset components, and stirring for dry mixing;
adding deionized water into the paste mixing machine, stirring, and wet mixing;
adding sulfuric acid into the paste mixer, stirring, and carrying out acid mixing;
and detecting the product after acid mixing and obtaining paste.
6. The preparation method of the silicon-based lead-acid storage battery positive electrode lead paste according to claim 5, characterized in that:
the lead powder, the tetrabasic lead sulfate crystal, the short fiber, the graphene, the colloidal graphite, the cobalt sulfate, the stannous sulfate and the antimony pentoxide comprise the following preset components in parts by weight:
70-85 parts of lead powder, 0.5-1.5 parts of tetrabasic lead sulfate crystal, 0.5-1.2 parts of short fiber, 0.1-0.3 part of graphene, 0.1-0.5 part of colloidal graphite, 0.01-0.05 part of cobalt sulfate, 0.01-0.05 part of stannous sulfate and 0.01-0.1 part of antimony pentoxide; the dry mixing time is 3-6 min.
7. The preparation method of the silicon-based lead-acid storage battery positive electrode lead paste according to claim 5, characterized in that: the deionized water comprises 7-15 parts by weight of the components, and the time for adding the deionized water is 1-3 min; the wet mixing time is 4-6 min.
8. The preparation method of the silicon-based lead-acid storage battery positive electrode lead paste according to claim 5, characterized in that: the sulfuric acid comprises 5-8 parts by weight of sulfuric acid, the time for adding the sulfuric acid is 5-10 min, and the acid mixing time is 6-12 min.
9. The preparation method of the silicon-based lead-acid storage battery positive electrode lead paste according to claim 5, characterized in that: the temperature of the dry mixing, the wet mixing and the acid mixing is 50-70 ℃.
10. The preparation method of the silicon-based lead-acid storage battery positive electrode lead paste according to claim 5, characterized in that: the detection comprises apparent density detection, and the apparent density of the lead plaster is 4.10-4.45 g/mL; the paste discharge temperature was 45 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824249A (en) * | 2022-05-24 | 2022-07-29 | 天能电池集团股份有限公司 | Lead storage battery positive plate lead paste and preparation method thereof, and lead storage battery |
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| US5368960A (en) * | 1993-07-23 | 1994-11-29 | Rowlette; John J. | Utilization efficiencies by using high sulfate starting materials |
| CN105958015A (en) * | 2016-06-27 | 2016-09-21 | 渤海大学 | Method for preparing composite active material bipolar electrode for bipolar lead-acid battery |
| CN112151776A (en) * | 2020-08-21 | 2020-12-29 | 安徽理士电源技术有限公司 | Long-life silicon-based bipolar lead storage battery anode lead paste and preparation method thereof |
| CN112191460A (en) * | 2020-08-21 | 2021-01-08 | 安徽理士电源技术有限公司 | Positive plate coating tool and method for long-life silicon-based bipolar lead storage battery |
| CN113178574A (en) * | 2021-04-28 | 2021-07-27 | 浙江巨江电源制造有限公司 | Positive pole lead plaster of lead-acid storage battery and bipolar horizontal storage battery containing positive pole lead plaster |
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2021
- 2021-08-09 CN CN202110907028.3A patent/CN113745501A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5368960A (en) * | 1993-07-23 | 1994-11-29 | Rowlette; John J. | Utilization efficiencies by using high sulfate starting materials |
| CN105958015A (en) * | 2016-06-27 | 2016-09-21 | 渤海大学 | Method for preparing composite active material bipolar electrode for bipolar lead-acid battery |
| CN112151776A (en) * | 2020-08-21 | 2020-12-29 | 安徽理士电源技术有限公司 | Long-life silicon-based bipolar lead storage battery anode lead paste and preparation method thereof |
| CN112191460A (en) * | 2020-08-21 | 2021-01-08 | 安徽理士电源技术有限公司 | Positive plate coating tool and method for long-life silicon-based bipolar lead storage battery |
| CN113178574A (en) * | 2021-04-28 | 2021-07-27 | 浙江巨江电源制造有限公司 | Positive pole lead plaster of lead-acid storage battery and bipolar horizontal storage battery containing positive pole lead plaster |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114824249A (en) * | 2022-05-24 | 2022-07-29 | 天能电池集团股份有限公司 | Lead storage battery positive plate lead paste and preparation method thereof, and lead storage battery |
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