CN107290292B - Method for detecting dispersion effect of additive in lead-acid storage battery in lead plaster - Google Patents
Method for detecting dispersion effect of additive in lead-acid storage battery in lead plaster Download PDFInfo
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Abstract
The invention relates to the technical field of lead-acid storage batteries, and particularly discloses a method for detecting the dispersion effect of an additive in a lead-acid storage battery in lead plaster, which comprises the steps of collecting a lead plaster sample to prepare a solution, measuring the content of Ba in filtrate by an atomic absorption spectrometer, calculating the mass N of Ba contained in the lead plaster sample of unit mass, then calculating the average value M and standard deviation S of N of all lead plaster samples, calculating a standard deviation rate S, reflecting the uniformity degree of the dispersion of the additive by the standard deviation rate S, enabling a sampling polar plate to be not in accordance with requirements if the standard deviation rate is greater than a set value, enabling the sampling polar plate to be in accordance with requirements if the standard deviation rate is less than or equal to the set value, enabling the additive to be uniformly dispersed if the standard deviation rate is smaller if different sampling polar plates are particularly the standard deviation rate is less than the set value, and accurately, intuitively, provides test judgment basis for improving the additive dispersion process.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to a method for detecting the dispersion effect of an additive in a lead paste in a lead-acid storage battery.
Background
The lead-acid accumulator is a charging power supply with stable performance and high safety, and its production process includes the procedures of making lead powder, making plate grid, making lead paste, coating polar plate, solidifying and drying polar plate, forming polar plate and assembling cell. The additive is an important polar plate auxiliary material of the lead-acid storage battery, comprises barium sulfate, sodium lignosulphonate and the like, and is added into the lead plaster in the lead plaster preparation process and coated on the green polar plate. The dispersion uniformity of the additive determines the quality stability of the battery, and whether the additive is uniformly dispersed or not only indicates the quality of lead paste in the lead-acid storage battery, but also reflects whether the existing additive dispersion process needs to be improved or not to a certain extent. However, the apparent density of the lead paste is detected in the existing lead paste and manufacturing process, so that the dispersion effect of the additive cannot be accurately reflected. Therefore, it is necessary to establish a detection method for accurately evaluating the dispersion effect of the additive, so as to improve the stability of the lead-acid storage battery.
Disclosure of Invention
Aiming at the problem that the dispersion effect of the additive of a lead plaster polar plate in the lead-acid storage battery cannot be accurately and effectively detected and evaluated, the invention aims to provide the method for detecting the dispersion effect of the additive in the lead plaster in the lead-acid storage battery, which can accurately, visually and quickly detect the dispersion effect of the additive in the lead plaster, is beneficial to improving the stability of the lead-acid storage battery and also provides a test judgment basis for improving the dispersion process of the additive.
The invention provides the following technical scheme:
a method for detecting the dispersion effect of an additive in lead-acid storage batteries in lead paste comprises the following steps:
(1) preparing test sample containing barium sulfate BaSO4Adding the additive into lead powder, uniformly mixing to prepare lead plaster, coating the lead plaster on a green polar plate, curing to prepare a sampling polar plate, marking a sampling position on the sampling polar plate and collecting a lead plaster sample;
(2) preparing test liquid, calcining the lead plaster sample, and dissolving in sulfuric acid H2SO4Ultrafiltering the solution, and diluting the filtrate to a constant volume to obtain a test solution;
(3) preparing standard solution, and calculating barium ion Ba according to the theoretical content of barium Ba in the lead paste2+C to prepare BaSO with 8-15 concentration gradients4Standard solution of Ba in the sample2+At a concentration of BaSO4The concentration gradient range of the standard solution;
(4) mixing BaSO4The standard solution is placed on an atomic absorption spectrometer to test BaSO with different concentrations4The absorbance lambda of the standard solution is obtained according to the test result2+A linear regression equation of concentration of (a);
(5) respectively placing the test solutions prepared from different lead plaster samples on an atomic absorption spectrometer for testing to obtain absorbance lambda, and then calculating Ba in the test solutions according to the linear regression equation in the step (4)2+The concentration of (3) C;
(6) from Ba in step (5)2+Concentration C, volume of test liquid and lead paste sampleCalculating the mass N mg/g of Ba contained in the lead plaster sample of unit mass;
(7) calculating the average value M and standard deviation S of the mass of Ba contained in the same sampling polar plate, wherein M is (∑ N)/N, S is [ (∑ N-M)2)/(n-1)]1/2N is the number of sampling positions;
(8) then calculating a standard deviation rate S, wherein S is S/M multiplied by 100%, comparing the standard deviation rate with a set value, if the standard deviation rate is greater than the set value, the sampling polar plate does not meet the requirement, and if the standard deviation rate is less than or equal to the set value, the sampling polar plate meets the requirement;
(9) and respectively calculating the s values of different sampling polar plates according to the steps, and comparing the dispersion effects of the additives on different polar plates by using s, wherein the smaller s is, the more uniform the additive distribution is, and the larger s is, the more dispersed the additive distribution is.
The method for detecting the dispersion effect of the additive in the lead-acid storage battery accurately reflects the distribution condition of the additive by quantitatively calculating the content distribution of Ba at different positions on a sampling polar plate, firstly, collecting a lead paste sample on a green polar plate to prepare a solution, then, carrying out ultrafiltration and volume-fixing on a filtrate, measuring the Ba content in the filtrate by an atomic absorption spectrometer, further calculating the mass N of Ba contained in the lead paste sample of unit mass, then, calculating the average value M and the standard deviation S of N of all the lead paste samples, and then, calculating the standard deviation rate S. For a sampling polar plate, if the standard deviation rate is greater than a set value, the sampling polar plate is not in accordance with the requirement, if the standard deviation rate is less than or equal to the set value, the sampling polar plate is in accordance with the requirement, for different sampling polar plates, especially when the standard deviation rates are less than the set value, the smaller the standard deviation rate is, the more uniform the additive is dispersed, and the more reasonable the additive process adopted by the sampling polar plate is reflected. The detection method is suitable for the detection of BaSO4Is also suitable for quantitatively adding BaSO into the additive4Then the dispersion effect of the additive in the lead plaster can be accurately, visually and quickly determined by detection, and the stability of the lead-acid storage battery can be improvedAnd the qualitative characteristic also provides a test judgment basis for improving the additive dispersion process.
As an improvement of the method of the present invention, the method for labeling the sampling site in step (1) is as follows: two diagonal lines are made on the sampling polar plate, the midpoint of a connecting line of the intersection point of the two diagonal lines and the vertex of the sampling polar plate is taken as a circle center, 1/8 lengths of the diagonal lines are taken as radiuses to make a circle, the two intersection points of the circle and the diagonal lines and the intersection points of the two diagonal lines are sampling positions, and each sampling polar plate has 9 sampling positions. Therefore, sampling in a large range can be covered on the sampling polar plate, and the distribution condition of the additive in the lead plaster can be accurately reflected by the detection result.
As an improvement of the method, in the step (2), the calcining temperature is 600-700 ℃, the calcining time is 60-90 minutes, and H is2SO4The concentration of the solution is 2-4 mol/L, and the adding volume is 50-80 mL. Organic matters and combined moisture in the sample are removed through calcination, and detection interference is removed.
As an improvement of the method of the invention, the filter membrane used in the ultrafiltration is an acetate fiber membrane with the pore diameter of 0.45 mu m or a polyvinylidene fluoride membrane with the pore diameter of 0.45 mu m. The adsorption quantity of the substances in the solution is minimum, and the detection accuracy is ensured.
As an improvement of the process of the present invention, BaSO in step (3)4Ba calculated from the mean concentration or the mean of the two mean concentrations of the standard solution and the theoretical content of Ba in the lead paste2+The deviation of the concentration c of (2) is. + -. 5%. When BaSO4When the number of gradient concentrations of the standard solution is odd, BaSO4Ba calculated from the intermediate concentration of the standard solution and the theoretical content of Ba in the lead paste2+When the deviation of the concentration c of (B) is. + -. 5%, when BaSO4When the number of the gradient concentration of the standard solution is even, the BaSO4Ba calculated from the intermediate concentration of the standard solution and the theoretical content of Ba in the lead paste2+Has a deviation of + -5% so that the concentration of Ba in the lead paste sample is as high as possible in BaSO4The detection accuracy is improved within the gradient concentration range of the solution. Wherein Ba is calculated from the theoretical content of Ba in the lead paste2+The concentration c of (a) is calculated by the following method:
c ═ axw%/V, where a represents the mass of the lead paste sample, w% represents the mass fraction of Ba in the lead paste produced, and V represents the volumetric volume of the test solution.
As an improvement of the method, the set value in the step (8) is determined by the following method, 100-200 lead paste coated green plates with qualified quality are taken, s of each green plate is calculated according to the processes from the step (1) to the step (8), and then the average value of s is obtained to be the set value. The distribution effect of the additives in the sampling polar plate is measured by setting a set value, and a test judgment basis is provided for improving the additive dispersion process.
As an improvement of the method, the atomic absorption spectrometer is a graphite furnace atomic absorption spectrometer. The graphite furnace atomic absorption spectrometer has high sensitivity and the detection limit reaches 10-6～10-14Can measure 10-13g/ml order of magnitude, can accurately quantify the Ba content, and is particularly suitable for adding trace BaSO into the additive4And (6) detecting.
As an improvement of the method, the detection parameters of the graphite furnace atomic absorption spectrometer are as follows: the wavelength is 455.4nm, the slit width is 0.5nm, the lamp current is 10mA, the burner height is 8mm, and the temperature rise program is as follows: the temperature is increased at the rate of 10 ℃/s for 40s at the temperature of 25-120 ℃; the temperature is increased by 10 ℃/s at the temperature of 120-1700 ℃, and the temperature is kept for 30 s; the temperature is 1700 ℃ to 2700 ℃, the heating rate is 30 ℃/s, and the temperature is kept for 5 s; 2700-2800 deg.C, heating rate 10 deg.C/s, keeping for 5 s. The detection process has better signal-to-noise ratio, background interference is eliminated, and the absorbance of Ba is maximum.
The invention has the following beneficial effects
According to the method for detecting the dispersion effect of the additive in the lead-acid storage battery, the distribution condition of the additive is accurately reflected by quantitatively calculating the content distribution of Ba at different positions on the sampling polar plate, the dispersion effect of the additive in the lead-acid storage battery can be accurately, visually and quickly determined, the distribution condition of the additive on a single sampling polar plate is judged by setting a set value, the distribution condition of the additive on different sampling polar plates is judged by a standard deviation rate, the stability of the lead-acid storage battery is improved, and a test judgment basis is provided for improving the dispersion process of the additive.
Drawings
FIG. 1 is a sample position mark of a sample pad.
In the figure, 1 is a sampling polar plate, 11 is a sampling position ①, 12 is a sampling position ②, 13 is a sampling position ③, 14 is a sampling position ④, 15 is a sampling position ⑤, 16 is a sampling position ⑥, 17 is a sampling position ⑦, 18 is a sampling position ⑧, 19 is a sampling position ⑨.
Detailed Description
The following further describes the embodiments of the present invention.
The starting materials used in the present invention are commercially available or commonly used in the art, unless otherwise specified, and the methods in the following examples are conventional in the art, unless otherwise specified.
The atomic absorption spectrometer is preferably a graphite furnace atomic absorption spectrometer, and the detection parameters of the graphite furnace atomic absorption spectrometer are as follows: the wavelength is 455.4nm, the slit width is 0.5nm, the lamp current is 10mA, the burner height is 8mm, and the temperature rise program is as follows: the temperature is increased at the rate of 10 ℃/s for 40s at the temperature of 25-120 ℃; the temperature is increased by 10 ℃/s at the temperature of 120-1700 ℃, and the temperature is kept for 30 s; the temperature is 1700 ℃ to 2700 ℃, the heating rate is 30 ℃/s, and the temperature is kept for 5 s; 2700-2800 deg.C, heating rate 10 deg.C/s, keeping for 5 s.
Example 1
A method for detecting the dispersion effect of an additive in lead-acid storage batteries in lead paste comprises the following steps:
(1) preparing test sample containing barium sulfate BaSO4The additive is added into lead powder and evenly mixed to prepare lead plaster, the lead plaster is coated on a green polar plate and solidified to prepare a sampling polar plate, the sampling position is marked on the sampling polar plate, 1 plus or minus 0.5mg of a lead plaster sample is collected, and the preferable method for marking the sampling position is as follows: as shown in FIG. 1, two diagonal lines are made on the sampling plate 1, a circle is made by taking the midpoint of the connecting line of the intersection point of the two diagonal lines and the vertex of the sampling plate as the center of the circle and the 1/8 length of the diagonal line as the radius, the two intersection points of the circle and the diagonal line and the intersection point of the two diagonal lines are sampling positions, each sampling plate has 9 sampling positions, and each sampling position is respectivelySample position ① 11, sample position ② 12, sample position ③ 13, sample position ④ 14, sample position ⑤ 15, sample position ⑥ 16, sample position ⑦ 17, sample position ⑧ 18, sample position ⑨ 19;
(2) preparing a test solution, calcining a lead plaster sample at 600 ℃ for 60 minutes, and fully dissolving the lead plaster sample in 2mol/L sulfuric acid H2SO4Adding 50mL of the solution, then filtering the precipitate and ultrafiltering the filtrate, and fixing the volume of the filtrate to 1000mL to obtain a test solution, wherein the filter membrane used for ultrafiltration is an acetate fiber membrane with the pore diameter of 0.45 mu m;
(3) preparing standard solution, and calculating barium ion Ba according to the theoretical content of barium Ba in the lead paste2+C to prepare BaSO with 8 concentration gradients4Standard solution of Ba in the sample2+At a concentration of BaSO4The concentration gradient range of the standard solution is in a range of C ═ A x w%/V, A represents the mass of the lead plaster sample, w% represents the mass fraction of Ba in the lead plaster prepared by the neutralization, V represents the constant volume of the test solution, and BaSO is preferred4Average of two intermediate concentrations of standard solution and calculated Ba from the theoretical content of Ba in the lead paste2+The deviation of the concentration c of (a) is. + -. 5%;
(4) mixing BaSO4The standard solution is placed on an atomic absorption spectrometer to test BaSO with different concentrations4The absorbance lambda of the standard solution is obtained according to the test result2+Linear regression equation of concentration of (1), goodness of fit R2≥0.995；
(5) Respectively placing the test solutions prepared from different lead plaster samples on an atomic absorption spectrometer for testing to obtain absorbance lambda, and then calculating Ba in the test solutions according to the linear regression equation in the step (4)2+The concentration of (3) C;
(6) from Ba in step (5)2+Calculating the mass N mg/g of Ba contained in the lead plaster sample in unit mass according to the concentration C, the volume of the test solution and the mass of the lead plaster sample;
(7) calculating the average value M and standard deviation S of the mass of Ba contained in the same sampling polar plate, wherein M is (∑ N)/N, S is [ (∑ N-M)2)/(n-1)]1/2N is the number of sampling positions, wherein n is 9;
(8) then calculating a standard deviation rate S, wherein S is S/M multiplied by 100%, comparing the standard deviation rate with a set value, if the standard deviation rate is larger than the set value, the sampling polar plate does not meet the requirement, if the standard deviation rate is smaller than or equal to the set value, the sampling polar plate meets the requirement, wherein the set value is determined by the following method, 100 lead plaster coated green polar plates with qualified quality are taken, S of each green polar plate is respectively calculated according to the processes of the steps (1) to (8), then the average value of S is calculated to be the set value, and the set value is 5%;
(9) and respectively calculating the s values of different sampling polar plates according to the steps, and comparing the dispersion effects of the additives on different polar plates by using s, wherein the smaller s is, the more uniform the additive distribution is, and the larger s is, the more dispersed the additive distribution is.
Optionally 5 sampling plates, the results obtained by the above treatment are shown in table 1 below.
TABLE 1
As can be seen from table 1 above, compared with the set value of 5%, the sampling electrode plates except the sampling electrode plate 5 all meet the requirements, and meanwhile, the s value of the sampling electrode plate 2 is the smallest, the additive dispersion degree is the most uniform, and the sampling electrode plates 4, 1 and 3 are arranged behind the sampling electrode plate.
Example 2
A method for detecting the dispersion effect of an additive in lead-acid storage batteries in lead paste comprises the following steps:
(1) preparing test sample containing barium sulfate BaSO4The additive is added into lead powder and evenly mixed to prepare lead plaster, the lead plaster is coated on a green polar plate and solidified to prepare a sampling polar plate, the sampling position is marked on the sampling polar plate, 1 plus or minus 0.5mg of a lead plaster sample is collected, and the preferable method for marking the sampling position is as follows: as shown in FIG. 1, two diagonal lines are made on the sampling polar plate 1, a circle is made by taking the midpoint of the connecting line of the intersection point of two diagonal lines and the top point of the sampling polar plate as the center of the circle and the 1/8 length of the diagonal line as the radius, the two intersection points of the circle and the diagonal line and the intersection point of the two diagonal lines are sampling positions, and each sampling polar plate has 9 sampling positions which are respectively takenSample position ① 11, sample position ② 12, sample position ③ 13, sample position ④ 14, sample position ⑤ 15, sample position ⑥ 16, sample position ⑦ 17, sample position ⑧ 18, sample position ⑨ 19;
(2) preparing a test solution, calcining a lead plaster sample at 650 ℃ for 75 minutes, and fully dissolving the lead plaster sample in 3mol/L sulfuric acid H2SO4Adding 65mL of the solution, then filtering the precipitate and ultrafiltering the filtrate, and fixing the volume of the filtrate to 1000mL to obtain a test solution, wherein the filter membrane used for ultrafiltration is a polyvinylidene fluoride membrane with the pore diameter of 0.45 mu m;
(3) preparing standard solution, and calculating barium ion Ba according to the theoretical content of barium Ba in the lead paste2+C to prepare BaSO with 12 concentration gradients4Standard solution of Ba in the sample2+At a concentration of BaSO4The concentration gradient range of the standard solution is in a range of C ═ A x w%/V, A represents the mass of the lead plaster sample, w% represents the mass fraction of Ba in the lead plaster prepared by the neutralization, V represents the constant volume of the test solution, and BaSO is preferred4Average value of two intermediate concentrations of standard solution and calculated Ba from theoretical content of Ba in lead paste2+The deviation of the concentration c of (a) is. + -. 5%;
(4) mixing BaSO4The standard solution is placed on an atomic absorption spectrometer to test BaSO with different concentrations4The absorbance lambda of the standard solution is obtained according to the test result2+Linear regression equation of concentration of (1), goodness of fit R2≥0.995；
(5) Respectively placing the test solutions prepared from different lead plaster samples on an atomic absorption spectrometer for testing to obtain absorbance lambda, and then calculating Ba in the test solutions according to the linear regression equation in the step (4)2+The concentration of (3) C;
(6) from Ba in step (5)2+Calculating the mass N mg/g of Ba contained in the lead plaster sample in unit mass according to the concentration C, the volume of the test solution and the mass of the lead plaster sample;
(7) calculating the average value M and standard deviation S of the mass of Ba contained in the same sampling polar plate, wherein M is (∑ N)/N, S is [ (∑ N-M)2)/(n-1)]1/2N is the number of sampling positions, wherein n is 9;
(8) then calculating a standard deviation rate S, wherein S is S/M multiplied by 100%, comparing the standard deviation rate with a set value, if the standard deviation rate is larger than the set value, the sampling polar plate does not meet the requirement, if the standard deviation rate is smaller than or equal to the set value, the sampling polar plate meets the requirement, wherein the set value is determined by the following method, taking 150 lead plaster coated green polar plates with qualified quality, respectively calculating S of each green polar plate according to the processes of the steps (1) to (8), and then solving the average value of S as the set value, wherein the set value is 5%;
(9) and respectively calculating the s values of different sampling polar plates according to the steps, and comparing the dispersion effects of the additives on different polar plates by using s, wherein the smaller s is, the more uniform the additive distribution is, and the larger s is, the more dispersed the additive distribution is.
Optionally 5 sampling plates, the results obtained by the above treatment are shown in table 2 below.
TABLE 2
As can be seen from table 2 above, the s values of the sampling plates 6, 7, 8, 9, and 10 are 8.306%, 3.617%, 4.567%, 5.052%, and 4.966%, respectively, and compared with the set value of 5%, the sampling plates 6 and 9 do not meet the requirements, the additive is dispersed uniformly to a lesser extent, the additive is dispersed uniformly in the sampling plates 7, 8, and 10, and the additive is dispersed uniformly in the sampling plate 7 because the s value of the sampling plate 7 is the smallest.
The results of the treatment of the test solutions obtained from the 5 sampling plates in example 1 in steps (2) to (8) in example 2 are shown in Table 2-1.
TABLE 2-1
As can be seen from table 2-1, the sampling plate 5 does not meet the requirement of 5% of the set value, then the additive dispersion degree in the sampling plate 2 is most uniform, and the sampling plates 4, 1, and 3 are arranged in sequence, which is the same as the analysis conclusion in example 1, and shows that the detection method has good reproducibility.
Example 3
A method for detecting the dispersion effect of an additive in lead-acid storage batteries in lead paste comprises the following steps:
(1) preparing test sample containing barium sulfate BaSO4The additive is added into lead powder and evenly mixed to prepare lead plaster, the lead plaster is coated on a green polar plate and solidified to prepare a sampling polar plate, the sampling polar plate is marked with sampling positions and 1 +/-0.5 mg of a lead plaster sample, and the preferable method for marking the sampling positions comprises the following steps of making two diagonal lines on the sampling polar plate 1, making a circle by taking the midpoint of a connecting line between the intersection point of two diagonal lines and the top point of the sampling polar plate as the center of a circle and the length of 1/8 of the diagonal line as the radius, wherein the two intersection points of the circle and the diagonal line and the intersection point of the two diagonal lines are the sampling positions, and each sampling polar plate has 9 sampling positions which are respectively ① 11, ②, ③, ④, ⑤, ⑥, ⑦, ⑧ and ⑨;
(2) preparing a test solution, calcining a lead plaster sample at 700 ℃ for 90 minutes, and fully dissolving the lead plaster sample in 4mol/L sulfuric acid H2SO4Adding 80mL of the solution, then filtering the precipitate and ultrafiltering the filtrate, and fixing the volume of the filtrate to 1000mL to obtain a test solution, wherein the filter membrane used for ultrafiltration is an acetate fiber membrane with the pore diameter of 0.45 mu m;
(3) preparing standard solution, and calculating barium ion Ba according to the theoretical content of barium Ba in the lead paste2+C to prepare 15 BaSO with concentration gradients4Standard solution, in order, to make Ba in the test sample2+At a concentration of BaSO4The concentration gradient range of the standard solution is in a range of C ═ A x w%/V, A represents the mass of the lead plaster sample, w% represents the mass fraction of Ba in the lead plaster prepared by the neutralization, V represents the constant volume of the test solution, and BaSO is preferred4Ba calculated from the intermediate concentration of the standard solution and the theoretical content of Ba in the lead paste2+The deviation of the concentration c of (a) is. + -. 5%;
(4) mixing BaSO4The standard solution is placed on an atomic absorption spectrometer to test BaSO with different concentrations4Absorbance lambda of the standard solutionObtaining absorbance lambda-Ba according to the test result2+Linear regression equation of concentration of (1), goodness of fit R2≥0.995；
(5) Respectively placing the test solutions prepared from different lead plaster samples on an atomic absorption spectrometer for testing to obtain absorbance lambda, and then calculating Ba in the test solutions according to the linear regression equation in the step (4)2+The concentration of (3) C;
(6) from Ba in step (5)2+Calculating the mass N mg/g of Ba contained in the lead plaster sample in unit mass according to the concentration C, the volume of the test solution and the mass of the lead plaster sample;
(7) calculating the average value M and standard deviation S of the mass of Ba contained in the same sampling polar plate, wherein M is (∑ N)/N, S is [ (∑ N-M)2)/(n-1)]1/2N is the number of sampling positions, wherein n is 9;
(8) then calculating a standard deviation ratio S, wherein S is S/M multiplied by 100%, comparing the standard deviation ratio with a set value, if the standard deviation ratio is larger than the set value, the sampling polar plate does not meet the requirement, if the standard deviation ratio is smaller than or equal to the set value, the sampling polar plate meets the requirement, wherein the set value is determined by the following method, 200 lead plaster coated green polar plates with qualified quality are taken, S of each green polar plate is respectively calculated according to the processes of the steps (1) to (8), then the average value of S is calculated to be the set value, and the set value is 5%;
(9) and respectively calculating the s values of different sampling polar plates according to the steps, and comparing the dispersion effects of the additives on different polar plates by using s, wherein the smaller s is, the more uniform the additive distribution is, and the larger s is, the more dispersed the additive distribution is.
Optionally 5 sampling plates, the results obtained by the above treatment are shown in table 3 below.
TABLE 3
As can be seen from the above table, the s values of the sampling plates 11, 12, 13, 14, and 15 are 3.700%, 7.511%, 2.965%, 5.580%, and 6.648%, respectively, and compared with the set value of 5%, the sampling plates 12, 14, and 15 are unsatisfactory, the additive is dispersed to a poor degree, and the additive is dispersed to a relatively uniform degree in the sampling plates 11 and 13, and the s value of the sampling plate 13 is the smallest, which indicates that the additive is dispersed to a most uniform degree in the sampling plate 3.
The results of the treatment of the test solutions obtained from the 5 sampling plates in example 1 in steps (2) to (8) in example 3 are shown in Table 3-1.
TABLE 3-1
As can be seen from table 3-1, the sampling electrode plate 5 does not meet the requirement of 5% of the set value, the additive dispersion degree in the sampling electrode plate 2 is most uniform, and the sampling electrode plates 4, 1 and 3 are arranged in sequence, which is the same as the analysis conclusion in example 1, and shows that the detection method has good reproducibility.
Claims (6)
1. A method for detecting the dispersion effect of an additive in lead-acid storage batteries in lead paste comprises the following steps:
(1) preparing test sample containing barium sulfate BaSO4Adding the additive into lead powder, uniformly mixing to prepare lead plaster, coating the lead plaster on a green polar plate, curing to prepare a sampling polar plate, marking a sampling position on the sampling polar plate and collecting a lead plaster sample;
(2) preparing test liquid, calcining the lead plaster sample, and dissolving in sulfuric acid H2SO4Ultrafiltering the solution, and diluting the filtrate to a constant volume to obtain a test solution;
(3) preparing standard solution, and calculating barium ion Ba according to the theoretical content of barium Ba in the lead paste2+C to prepare BaSO with 8-15 concentration gradients4Standard solution of Ba in the sample2+At a concentration of BaSO4The concentration gradient range of the standard solution;
(4) mixing BaSO4The standard solution is placed on an atomic absorption spectrometer to test BaSO with different concentrations4The absorbance lambda of the standard solution is obtained according to the test result2+A linear regression equation of concentration of (a);
(5) respectively placing the test solutions prepared from different lead plaster samples on an atomic absorption spectrometer for testing to obtain absorbance lambda, and then calculating Ba in the test solutions according to the linear regression equation in the step (4)2+The concentration of (3) C;
(6) from Ba in step (5)2+Calculating the mass N mg/g of Ba contained in the lead plaster sample in unit mass according to the concentration C, the volume of the test solution and the mass of the lead plaster sample;
(7) calculating the average value M and standard deviation S of the mass of Ba contained in the same sampling polar plate, wherein M is (∑ N)/N, S is [ (∑ N-M)2)/(n-1)]1/2N is the number of sampling positions;
(8) then calculating a standard deviation rate S, wherein S is S/M multiplied by 100%, comparing the standard deviation rate with a set value, if the standard deviation rate is greater than the set value, the sampling polar plate does not meet the requirement, and if the standard deviation rate is less than or equal to the set value, the sampling polar plate meets the requirement;
(9) respectively calculating the s values of different sampling polar plates according to the steps, and comparing the dispersion effects of the additives on different polar plates by using s, wherein the smaller s is, the more uniform the additive distribution is, and the larger s is, the more dispersed the additive distribution is;
the method for marking the sampling position in the step (1) is as follows: making two diagonal lines on the sampling polar plate, taking the midpoint of a connecting line of the intersection point of the two diagonal lines and the top point of the sampling polar plate as a circle center, taking 1/8 lengths of the diagonal lines as a radius to make a circle, wherein the two intersection points of the circle and the diagonal lines and the intersection points of the two diagonal lines are sampling positions, and each sampling polar plate has 9 sampling positions;
BaSO in step (3)4Ba calculated from the mean concentration or the mean of the two mean concentrations of the standard solution and the theoretical content of Ba in the lead paste2+The deviation of the concentration c of (2) is. + -. 5%.
2. The method for detecting the dispersion effect of the additive in the lead-acid storage battery in the lead-acid paste according to claim 1, wherein the calcination temperature in the step (2) is 600-700 ℃, the calcination time is 60-90 minutes, and H is2SO4The concentration of the solution is 2-4 mol/L, and the adding volume is 50-80 mL.
3. The method for detecting the dispersion effect of the additive in the lead-acid storage battery in the lead paste according to claim 1, wherein the filter membrane used for ultrafiltration is an acetate fiber membrane with a pore size of 0.45 μm or a polyvinylidene fluoride membrane with a pore size of 0.45 μm.
4. The method for detecting the dispersion effect of the additive in the lead-acid storage battery according to claim 1, wherein the set value in the step (8) is determined by taking 100-200 lead paste-coated green plates with qualified quality, respectively calculating s of each green plate according to the processes from the step (1) to the step (8), and then calculating the average value of s to obtain the set value.
5. The method for detecting the dispersion effect of the additive in the lead-acid storage battery in the lead-acid paste according to any one of claims 1 to 4, wherein the atomic absorption spectrometer is a graphite furnace atomic absorption spectrometer.
6. The method for detecting the dispersion effect of the additive in the lead-acid storage battery in the lead-acid paste according to claim 5, wherein the detection parameters of the graphite furnace atomic absorption spectrometer are as follows: the wavelength is 455.4nm, the slit width is 0.5nm, the lamp current is 10mA, the burner height is 8mm, and the temperature rise program is as follows: the temperature is increased at the rate of 10 ℃/s for 40s at the temperature of 25-120 ℃; the temperature is increased by 10 ℃/s at the temperature of 120-1700 ℃, and the temperature is kept for 30 s; the temperature is 1700 ℃ to 2700 ℃, the heating rate is 30 ℃/s, and the temperature is kept for 5 s; 2700-2800 deg.C, heating rate 10 deg.C/s, keeping for 5 s.
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