CN107359312B - Preparation method of lead plaster and detection method of carbon material dispersion effect of lead plaster - Google Patents
Preparation method of lead plaster and detection method of carbon material dispersion effect of lead plaster Download PDFInfo
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- CN107359312B CN107359312B CN201710459761.7A CN201710459761A CN107359312B CN 107359312 B CN107359312 B CN 107359312B CN 201710459761 A CN201710459761 A CN 201710459761A CN 107359312 B CN107359312 B CN 107359312B
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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
- H01M4/16—Processes of manufacture
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/362—Composites
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 invention relates to the field of lead-acid storage battery manufacturing, in particular to a preparation method of lead plaster and a detection method of a carbon material dispersion effect of the lead plaster. A preparation method of lead plaster comprises the following steps of pretreating a carbon material, and then carrying out water mixing treatment and acid mixing treatment to obtain a finished lead plaster product. The invention provides a method for detecting the carbon material dispersion effect of lead plaster, which comprises the steps of grinding the lead plaster, coating the ground lead plaster on the surface of a green plate, standing for solidification, sampling, placing the sample in a test position, carrying out thermal analysis by using a differential scanning calorimeter to obtain the temperature and characteristic peak map of the sample, and obtaining a detection result after analysis. The invention has the beneficial effects that the technical scheme of the invention provides a preparation method of the lead plaster with uniformly dispersed carbon material and a detection method of the carbon material dispersion effect of the lead plaster, which has the advantages of rapid and accurate process, low cost, visual result and easy comparison.
Description
Technical Field
The invention relates to the field of lead-acid storage battery manufacturing, in particular to a preparation method of lead plaster and a detection method of a carbon material dispersion effect of the lead plaster.
Background
The production process of the lead-carbon battery for the electric bicycle mainly comprises the working procedures of manufacturing a grid, preparing lead plaster, coating a plate, curing and drying, assembling the battery, forming a polar plate and the like. The preparation process of the lead paste is an important, complex and difficult-to-control process in the production process of the lead-carbon battery, and the dispersion condition of the additive, the addition mode and the addition amount of the sulfuric acid and the water can influence the performance of the lead-carbon battery in the process. If the performance difference of the whole set of lead-carbon battery pack is too large, the lead-carbon battery pack is easy to disperse, the lead-carbon battery pack is easy to fail prematurely, and the service life is influenced. Therefore, the consistency of the lead-carbon battery needs to be improved so as to improve the performance and the service life of the whole lead-carbon battery pack. The dispersion condition of the additives in the lead-carbon battery is a main factor influencing the overall performance of the lead-carbon battery, and the carbon material has poor dispersibility and is easy to agglomerate, so that the improvement of the dispersion condition of the additives in the battery, particularly the carbon material, is an important way for improving the performance of the battery.
Chinese patent CN 103811752 a lead-carbon battery negative lead plaster and its preparation method, lead-carbon battery negative plate and lead-carbon battery disclose the following technical schemes: 100 parts of lead powder, 0.1-2 parts of barium sulfate, 0.01-2 parts of hydrogen evolution inhibitor, 50-100 parts of graphene oxide, 0.05-1 part of acetylene black, 1-4 parts of humic acid, 5-15 parts of red lead and 0.1-0.2 part of short fiber are poured into a container and are uniformly stirred to obtain a mixture, 12-21 parts of water are added into the mixture, 4-100 parts of sulfuric acid is added under the condition of stirring after the mixture is uniformly stirred, the mixture is stirred for 10-20 minutes, 0.1-8 parts of binder is added into the mixture after the sulfuric acid treatment, the mixture is uniformly stirred, and the apparent density of a mixed colloid is controlled to be 3.5-4.5 g/ml, so that the lead-carbon battery cathode lead paste is obtained. The disadvantages of the invention are: in the technical scheme, the additive, particularly the carbon material, is likely to be unevenly dispersed, so that the performance of the lead-carbon battery is affected, the performance of the whole set of lead-carbon battery pack is easily greatly different, the lead-carbon battery pack is easily dispersed, and the performance and the service life of the lead-carbon battery pack are affected.
At present, the dispersion effect of the carbon material in the lead-acid storage battery is mainly detected by adopting methods such as metallographic microscope observation or indirect display of data measured by a roughness tester, and the like, and the method for detecting the dispersion effect of the carbon material has the problems of long detection time, low detection accuracy, incapability of intuitively reflecting the dispersion effect of the carbon material in lead paste and the like. Chinese patent CN 106353352A discloses a method for detecting the dispersion effect of a carbon material in a lead-acid storage battery, which is to observe the dispersion effect of the carbon material in lead paste by combining an electron microscope energy spectrum element diagram before the treatment of a polar plate with a treated polar plate electron microscope diagram.
Therefore, a preparation method of the additive, particularly a lead plaster with uniformly dispersed carbon materials in the additive, and a detection method of the carbon material dispersion effect of the lead plaster, which has the advantages of rapid and accurate process, low cost, visual and easily-compared result, are needed at present.
Disclosure of Invention
The method for preparing the lead plaster with the uniformly dispersed carbon material and the method for detecting the carbon material dispersion effect of the lead plaster with the uniformly dispersed carbon material are provided, wherein the method is used for solving the problems that the dispersion of the carbon material of the lead plaster of the lead-carbon battery is not uniform, the performance of the lead-carbon battery is influenced, the performance of the lead-carbon battery is easily different from that of the whole set of lead-carbon battery, the lead-carbon battery is dispersed, and the performance and the service life of the lead-carbon battery are influenced. The invention adopts the following technical scheme:
a preparation method of lead paste comprises the following steps:
(1) carbon material pretreatment: putting a dispersing agent and a carbon material into an organic solvent in sequence to enable the carbon material and the dispersing agent to be completely soaked to obtain a mixture, then carrying out ultrasonic water bath treatment on the mixture to obtain a dispersion liquid, then carrying out high-pressure dispersion treatment on the dispersion liquid by using a high-pressure dispersion equipment to obtain a polymer dispersion liquid, stirring the polymer dispersion liquid for 0.5-1.2 hours at the temperature of 85-95 ℃ to obtain a stable dispersion liquid, filtering the stable dispersion liquid, collecting a precipitate, washing with water and drying to obtain powder;
(2) water mixing treatment: mixing the powder with water, adding short fibers, shearing and stirring for 1-2 minutes to obtain a mixed solution, and adding the mixed solution into lead powder to obtain a semi-finished lead plaster;
(3) acid mixing treatment: and adding sulfuric acid into the semi-finished lead plaster while stirring, and mixing with acid to obtain a finished lead plaster.
And (2) carrying out ultrasonic water bath on the mixture in the pretreatment process of the carbon material in the step (1), wherein ultrasonic waves are conducted in the liquid by the fluctuation above the human auditory acoustic frequency, and have the characteristics of high frequency, short wavelength and strong penetrating power, so that the ultrasonic waves have high energy. When the sound wave propagates in the mixture, the action of the longitudinal wave pushing medium can change the pressure in the liquid to generate countless tiny vacuum bubbles, which is called as 'cavity effect', because the sound wave is a longitudinal wave. In the invention, when the vapor bubble is exploded under pressure, strong impact energy can be generated, and the carbon materials bonded together in the vapor bubble can be scattered, so that the condition that the carbon materials are distributed unevenly in the lead plaster due to the mutual bonding of some carbon powder caused by surface acting force can be prevented, and the dispersion effect of the carbon materials in the lead plaster is enhanced.
Generally, short fibers are put into pure water to be stirred, so that the fibers can be visually found to be in a uniformly dispersed state, and the fibers are not changed greatly after being placed for a long time; however, there are often untreated short fibers which are poor in dispersion state in water and are dispersed by stirring, but float up soon to form a flocky layer. The phenomenon can affect the uneven dispersion state of the additive in the lead plaster and the performance of the battery, so that the short fibers are sheared and stirred in the water mixing step in the step (2), the short fibers and the additive can be evenly dispersed in the water under the action of shearing force, and compared with the existing dry stirring method, the method can solve the problem of uneven stirring of various powder materials, shorten the stirring time and improve the production efficiency.
Preferably, the dispersant is one or more of lignosulfonate, sulfonated polystyrene, naphthalene sulfonic acid formaldehyde condensate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone or polyacrylic acid.
The combination of the materials can help the carbon material to be better dispersed in the solvent, and the dispersion effect of the carbon material is improved.
Preferably, the organic solvent is one or more of methanol, ethanol, acetone or diethyl ether.
Preferably, the temperature of the water bath in the ultrasonic water bath treatment process in the step (1) is 58-70 ℃, and the ultrasonic time is 0.3-1 hour.
Preferably, the high-pressure dispersion treatment in the step (1) is performed under the condition that the air pressure value is 103-125 MPa, and the high-pressure dispersion treatment process is repeated for 2-3 times, wherein each treatment time is 3-5 min.
Firstly, the carbon material can be fully dispersed in the dispersing agent through repeated high-pressure dispersion treatment for 2-3 times, so that a polymer is formed, incomplete polymer formation is prevented, and the carbon material is dispersed more uniformly.
Preferably, the mixed solution in the step (2) is added to the lead powder in a spraying manner, and the adding rate of the spraying is 0.17-0.33 ml/s.
Preferably, the addition rate of sulfuric acid during the acid mixing in step (3) is as follows:
a, when the temperature of the semi-finished lead plaster is below 48 ℃, controlling the initial adding rate of sulfuric acid to be 0.17-0.22L/s,
b, when the temperature of the semi-finished lead plaster is between 48 and 57 ℃, adjusting the adding speed of the sulfuric acid to be 70 to 85 percent of the initial flow speed,
c, when the temperature of the semi-finished lead plaster is 57-68 ℃, adjusting the adding speed of the sulfuric acid to be 50-60% of the initial flow speed,
d, when the temperature of the semi-finished lead plaster rises to 68-70 ℃, reducing the flow rate to maintain the temperature of the semi-finished lead plaster for 3-5 min,
and e, after adding sulfuric acid, continuing stirring for 5-8 minutes until the temperature of the semi-finished lead plaster product is reduced to 43-50 ℃, and obtaining a finished lead plaster product.
According to the scheme, a higher sulfuric acid adding rate is adopted for reaction, the reaction is violent at this time, the sulfuric acid reacts with lead oxide in a lead plaster semi-finished product to form lead sulfate, the reaction releases heat to cause temperature rise, when the temperature reaches 48-57 ℃, the lead sulfate generated by the reaction further reacts to generate tribasic lead sulfate, and as side reactions occur in the process, stereoisomer byproducts of the tribasic lead sulfate can damage the structure of tribasic lead sulfate crystals and influence the performance of a battery, the sulfuric acid adding rate is reduced, so that the generation rate of the lead sulfate can be reduced, and the generation of overlarge lead sulfate crystals is prevented; on the other hand, the amount of lead sulfate can be reduced in the reaction stage, the reduction of the amount of lead sulfate in the reaction stage can prevent side reactions from occurring, and is beneficial to improving the purity of tribasic lead sulfate, when the temperature rises to 68-70 ℃, tribasic lead sulfate is further generated by the reaction, tribasic lead sulfate crystals are increased, the flow rate is further reduced to control the temperature, the phenomenon that the crystals are too large due to overhigh temperature and the generated crystals are fine and stable is prevented, and the stirring is continued after the reaction is finished, so that on one hand, the generation of fine crystals can be promoted, on the other hand, the carbon material can be uniformly mixed into the crystals, and the uniform dispersion of the carbon material is ensured. This scheme does not use heating device in the use, can play the effect of saving cost on the one hand, and on the other hand has increased reaction time, helps controlling reaction temperature, makes the crystal that obtains tiny compact, can improve the cycle life of battery like this.
A method for detecting the dispersion effect of a carbon material of a lead paste comprises the following steps:
(1) preparing a sample: grinding lead paste, coating the ground lead paste on the surface of a green plate, and standing to solidify the lead paste;
(2) sampling: selecting lead plaster on the cured green plate by adopting a standard sampling method, sampling samples containing samples of the same green plate at different positions and samples of the green plate at different plaster coating time periods, and then placing active substance samples of the green plate in a testing position;
(3) DSC thermal analysis: and carrying out thermal analysis by a differential scanning calorimeter to obtain a temperature and characteristic peak map of the sample, obtaining a differential thermal analysis curve of the lead plaster after analysis, and then obtaining energy change in the heat release process through linear integral analysis to obtain a detection result.
According to the invention, the results of the dispersion state of the carbon material can be intuitively and quickly obtained by drawing and comparing differential thermal analysis curves of different samples and then comparing the standard deviation rates of the obtained results, so that the method is more convenient, accurate and easy to compare compared with the prior art.
Preferably, the DSC thermal analysis process in the step (3) is carried out in a nitrogen atmosphere, the temperature rise rate is 15-22 ℃/min, and the end temperature is 700-1100 ℃.
The finishing temperature adopted in the invention is 700-1000 ℃, so that the carbon material can be completely burnt out, and the result is more accurate.
Preferably, the mass of the sample and the blank sample in the sampling process in the step (2) is 50-600 mg.
The invention has the beneficial effects that: (1) the battery produced by the lead plaster with the carbon material uniformly dispersed (2) has long service life (2) the method for detecting the carbon material dispersion effect of the lead plaster has the advantages of rapid and accurate process and low cost (3) the method for detecting the carbon material dispersion effect of the lead plaster has visual and easily-compared detection results.
Detailed Description
The invention is further explained below with reference to specific embodiments:
example 1
A preparation method of lead plaster comprises the following steps:
(1) carbon material pretreatment: sequentially putting lignosulfonate and a carbon material into acetone to enable the carbon material and lignosulfonate to be completely soaked to obtain a mixture, then carrying out ultrasonic water bath treatment on the mixture, wherein the water bath temperature is 58 ℃ and the ultrasonic time is 0.3 hour in the ultrasonic water bath treatment process to obtain a dispersion liquid, then carrying out high-pressure dispersion treatment on the dispersion liquid by using a high-pressure dispersion equipment instrument, repeating the high-pressure dispersion treatment process for 2 times, the air pressure value is 103MPa, the treatment time is 3 minutes each time to obtain a polymer dispersion liquid, stirring the polymer dispersion liquid for 0.5 hour at 85 ℃ to obtain a stable dispersion liquid, filtering the stable dispersion liquid, collecting precipitates, washing with water and drying to obtain powder;
(2) water mixing treatment: mixing the powder with water, adding short fibers, shearing and stirring for 1 minute to obtain a mixed solution, adding the mixed solution into lead powder in a spraying manner, wherein the adding speed of spraying is 0.17ml/s, and thus obtaining a semi-finished lead plaster product;
(3) acid mixing treatment: adding sulfuric acid into the semi-finished lead plaster while stirring, wherein the adding rate of the sulfuric acid is as follows:
a when the temperature of the semi-finished lead plaster is below 48 ℃, controlling the initial adding rate of the sulfuric acid to be 0.17L/s,
b, when the temperature of the semi-finished lead plaster is between 48 and 57 ℃, adjusting the adding speed of the sulfuric acid to be 70 percent of the initial flow speed,
c, when the temperature of the semi-finished lead plaster is 57-68 ℃, adjusting the adding speed of the sulfuric acid to be 50% of the initial flow rate,
d, when the temperature of the semi-finished lead plaster rises to 68-70 ℃, reducing the flow rate to maintain the temperature of the semi-finished lead plaster for 3min,
e, after adding the sulfuric acid, continuing stirring for 5 minutes until the temperature of the semi-finished lead plaster is reduced to 43 ℃, and obtaining a finished lead plaster.
And then detecting the carbon material dispersion effect of the obtained lead plaster finished product, wherein the steps are as follows:
(1) preparing a sample: grinding lead paste, coating the ground lead paste on the surface of a green plate, and standing to solidify the lead paste;
(2) sampling: selecting lead plaster on the cured green plate by adopting a standard sampling method, sampling 500mg of each sample, wherein each sample comprises samples on the green plate at different positions of the same green plate and samples on the green plate in different plaster coating time periods, and then placing active substance samples of the green plate in a testing position;
(3) DSC thermal analysis: thermal analysis was performed by a differential scanning calorimeter, the DSC thermal analysis process was performed under a nitrogen atmosphere, the temperature rise rate was 22 ℃/min, and the end temperature was 1000 ℃.
And obtaining the temperature and characteristic peak map of the sample, obtaining a differential thermal analysis curve of the lead plaster after analysis, and obtaining the energy change in the heat release process through linear integral analysis to obtain a detection result.
Example 2
A preparation method of lead plaster comprises the following steps:
(1) carbon material pretreatment: sequentially putting lignosulfonate and a carbon material into acetone to enable the carbon material and lignosulfonate to be completely soaked to obtain a mixture, then carrying out ultrasonic water bath treatment on the mixture, wherein the water bath temperature is 70 ℃ and the ultrasonic time is 1 hour in the ultrasonic water bath treatment process to obtain a dispersion liquid, then carrying out high-pressure dispersion treatment on the dispersion liquid by using a high-pressure dispersion equipment instrument, the air pressure value is 103MPa, the high-pressure dispersion treatment process is repeated for 3 times, the treatment time is 5 minutes each time to obtain a polymer dispersion liquid, stirring the polymer dispersion liquid for 1.2 hours at 95 ℃ to obtain a stable dispersion liquid, filtering the stable dispersion liquid, collecting precipitates, washing with water and drying to obtain powder;
(2) water mixing treatment: mixing the powder with water, adding short fibers, shearing and stirring for 2 minutes to obtain a mixed solution, adding the mixed solution into lead powder in a spraying manner, wherein the spraying addition rate is 0.33ml/s, and thus obtaining a semi-finished lead plaster product;
(3) acid mixing treatment: adding sulfuric acid into the semi-finished lead plaster while stirring, wherein the adding rate of the sulfuric acid is as follows:
a when the temperature of the semi-finished lead plaster is below 48 ℃, controlling the initial adding rate of the sulfuric acid to be 0.22L/s,
b, when the temperature of the semi-finished lead plaster is between 48 and 57 ℃, adjusting the adding speed of the sulfuric acid to be 85 percent of the initial flow rate,
c, when the temperature of the semi-finished lead plaster is 57-68 ℃, adjusting the adding speed of the sulfuric acid to be 60% of the initial flow speed,
d, when the temperature of the semi-finished lead plaster rises to 68-70 ℃, reducing the flow rate to maintain the temperature of the semi-finished lead plaster for 5min,
e, after adding the sulfuric acid, continuing stirring for 8 minutes until the temperature of the semi-finished lead plaster is reduced to 50 ℃ to obtain a finished lead plaster.
And then detecting the carbon material dispersion effect of the obtained lead plaster finished product, wherein the steps are as follows:
(1) preparing a sample: grinding lead paste, coating the ground lead paste on the surface of a green plate, and standing to solidify the lead paste;
(2) sampling: selecting lead plaster on the cured green plate by adopting a standard sampling method, sampling 500mg of each sample, wherein each sample comprises samples on the green plate at different positions of the same green plate and samples on the green plate in different plaster coating time periods, and then placing active substance samples of the green plate in a testing position;
(3) DSC thermal analysis: thermal analysis was performed by a differential scanning calorimeter, the DSC thermal analysis process was performed under a nitrogen atmosphere, the temperature rise rate was 22 ℃/min, and the end temperature was 1000 ℃.
And obtaining the temperature and characteristic peak map of the sample, obtaining a differential thermal analysis curve of the lead plaster after analysis, and obtaining the energy change in the heat release process through linear integral analysis to obtain a detection result.
Example 3
A preparation method of lead plaster comprises the following steps:
(1) carbon material pretreatment: sequentially putting lignosulfonate and a carbon material into acetone to enable the carbon material and lignosulfonate to be completely soaked to obtain a mixture, then carrying out ultrasonic water bath treatment on the mixture, wherein the water bath temperature is 70 ℃ and the ultrasonic time is 1 hour in the ultrasonic water bath treatment process to obtain a dispersion liquid, then carrying out high-pressure dispersion treatment on the dispersion liquid by using a high-pressure dispersion equipment instrument, the air pressure value is 103MPa, the high-pressure dispersion treatment process is repeated for 2 times, the treatment time is 4 minutes each time to obtain a polymer dispersion liquid, stirring the polymer dispersion liquid for 1 hour at 90 ℃ to obtain a stable dispersion liquid, filtering the stable dispersion liquid, collecting precipitates, washing with water and drying to obtain powder;
(2) water mixing treatment: mixing the powder with water, adding short fibers, shearing and stirring for 2 minutes to obtain a mixed solution, adding the mixed solution into lead powder in a spraying manner, wherein the spraying addition rate is 0.25ml/s, and thus obtaining a semi-finished lead plaster product;
(3) acid mixing treatment: adding sulfuric acid into the semi-finished lead plaster while stirring, wherein the adding rate of the sulfuric acid is as follows:
a when the temperature of the semi-finished lead plaster is below 48 ℃, controlling the initial adding rate of the sulfuric acid to be 0.21L/s,
b, when the temperature of the semi-finished lead plaster is between 48 and 57 ℃, adjusting the adding speed of the sulfuric acid to 78 percent of the initial flow speed,
c, when the temperature of the semi-finished lead plaster is 57-68 ℃, adjusting the adding speed of the sulfuric acid to 55% of the initial flow rate,
d, when the temperature of the semi-finished lead plaster rises to 68-70 ℃, reducing the flow rate to maintain the temperature of the semi-finished lead plaster for 4min,
e, after adding the sulfuric acid, continuing stirring for 7 minutes until the temperature of the semi-finished lead plaster is reduced to 45 ℃ to obtain a finished lead plaster.
And then detecting the carbon material dispersion effect of the obtained lead plaster finished product, wherein the steps are as follows:
(1) preparing a sample: grinding lead paste, coating the ground lead paste on the surface of a green plate, and standing to solidify the lead paste;
(2) sampling: selecting lead plaster on the cured green plate by adopting a standard sampling method, sampling 500mg of each sample, wherein each sample comprises samples on the green plate at different positions of the same green plate and samples on the green plate in different plaster coating time periods, and then placing active substance samples of the green plate in a testing position;
(3) DSC thermal analysis: thermal analysis was performed by a differential scanning calorimeter, the DSC thermal analysis process was performed under a nitrogen atmosphere, the temperature rise rate was 22 ℃/min, and the end temperature was 1000 ℃.
Obtaining the temperature and characteristic peak atlas of the sample, obtaining the differential thermal analysis curve of the lead plaster after analysis, and obtaining the energy change in the heat release process through linear integral analysis to obtain the detection result.
The results of the tests performed on the plate samples of examples 1-3 for the same time period are as follows:
for the comparison results of samples at different positions of the same polar plate, we can see that the standard deviation rate of the weight reduction result is small, so that the result that the dispersion result of the carbon material on each polar plate is good can be obtained, and for the condition that the content difference of the carbon material existing among different polar plates is large, the influence of the content difference of the carbon material among different polar plates on the battery performance is small, so that the influence can be ignored. Generally speaking, the method provided by the invention can enable the carbon material in the lead paste to be uniformly distributed, thereby prolonging the service life of the battery, and the detection method provided by the invention can intuitively, simply and conveniently reflect whether the carbon material in the lead paste is uniformly distributed, thereby achieving the purpose of the invention.
Claims (2)
1. A method for detecting the dispersion effect of a carbon material of lead paste of a lead-carbon battery is characterized by comprising the following steps:
(1) preparing a sample: grinding lead paste, coating the ground lead paste on the surface of a green plate, and standing to solidify the lead paste;
(2) sampling: selecting lead plaster on the cured green plate by adopting a standard sampling method, sampling samples containing samples of the same green plate at different positions and samples of the green plate at different plaster coating time periods, and then placing active substance samples of the green plate in a testing position;
(3) DSC thermal analysis: carrying out thermal analysis by a differential scanning calorimeter to obtain a temperature and characteristic peak map of a sample, obtaining a differential thermal analysis curve of the lead plaster after analysis, and then obtaining energy change in a heat release process through linear integral analysis to obtain a detection result;
wherein, the DSC thermal analysis process in the step (3) is carried out in a nitrogen atmosphere, the heating rate is 15-22 ℃/min, and the finishing temperature is 700-1100 ℃.
2. The method for detecting the dispersion effect of the carbon material in the lead paste of the lead-carbon battery according to claim 1, wherein the method comprises the following steps: and (3) the mass of the sample and the blank sample in the sampling process in the step (2) is 50-600 mg.
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| CN108919130B (en) * | 2018-06-12 | 2021-01-01 | 风帆有限责任公司 | Method for detecting dispersion uniformity of additive in negative lead paste of lead-acid storage battery |
| CN111525195B (en) * | 2019-02-01 | 2022-04-26 | 骆驼集团蓄电池研究院有限公司 | Maintenance-free lead-acid storage battery with excellent deep cycle life and production method thereof |
| CN114558490A (en) * | 2022-02-24 | 2022-05-31 | 天能电池集团(马鞍山)新能源科技有限公司 | Negative mixing paste emulsified slurry adding method and mixing method applying negative mixing paste emulsified slurry |
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| CN101937991A (en) * | 2010-05-07 | 2011-01-05 | 张家口保胜新能源科技有限公司 | High-energy lead-acid storage battery cathode plate diachylon and preparation method thereof |
| CN102180458A (en) * | 2011-03-25 | 2011-09-14 | 深圳市贝特瑞纳米科技有限公司 | Nano-carbon material dispersion liquid and preparation method and equipment thereof |
| CN103682329A (en) * | 2013-11-15 | 2014-03-26 | 超威电源有限公司 | Internal formation lead plaster preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101937991A (en) * | 2010-05-07 | 2011-01-05 | 张家口保胜新能源科技有限公司 | High-energy lead-acid storage battery cathode plate diachylon and preparation method thereof |
| CN102180458A (en) * | 2011-03-25 | 2011-09-14 | 深圳市贝特瑞纳米科技有限公司 | Nano-carbon material dispersion liquid and preparation method and equipment thereof |
| CN103682329A (en) * | 2013-11-15 | 2014-03-26 | 超威电源有限公司 | Internal formation lead plaster preparation process |
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