CN112945870B - Detection method and application of lead content - Google Patents
Detection method and application of lead content Download PDFInfo
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- CN112945870B CN112945870B CN201911174664.9A CN201911174664A CN112945870B CN 112945870 B CN112945870 B CN 112945870B CN 201911174664 A CN201911174664 A CN 201911174664A CN 112945870 B CN112945870 B CN 112945870B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
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Abstract
The invention provides a method for detecting lead content, which comprises the following steps: (1) Carrying out first ball milling on a sample to be detected in an organic solvent to obtain a prefabricated product A; (2) Performing second ball milling on the prefabricated product A obtained in the step (1) under the action of alkali and an organic solvent to obtain a prefabricated product B; (3) Performing third ball milling on the prefabricated product B obtained in the step (2) under the action of dilute nitric acid and an organic solvent to obtain a prefabricated product C; (4) Performing ball milling on the prefabricated product C obtained in the step (3) for the fourth time under the action of concentrated sulfuric acid to obtain a prefabricated product D; (5) Testing the content of lead in the preform D obtained in the step (4) by adopting a spectrophotometry method so as to calculate the content of lead in a sample to be tested; the interference of impurity elements in the battery piece is removed in a ball-milling reaction mode, the impurity removal, concentration and purification of the target lead element are achieved, and the accurate measurement of the lead content in the battery piece is completed by controlling the process conditions.
Description
Technical Field
The invention belongs to the field of analysis and detection, and relates to a detection method and application of lead content.
Background
Of all known toxic substances, the most well-documented is lead. Ancient books have recorded that the use of lead pipes to transport drinking water is considered dangerous. There are many ways that the public can come into contact with lead. The public is mainly concerned with the problem of lead in petroleum products. Pigments containing lead, especially some old grades of pigments containing higher lead, have caused many deaths, and therefore some countries have specifically set environmental standards that regulate the lead content in pigments to within 600 PPM.
Some countries have no standards yet, but labels are attached to warn users when high-lead-content pigments are sold in the market. Lead residues are also found in the food, either in the air to reduce contamination of the food, or on the can scalp to contaminate the canned food. Another important source of lead is lead tubing. Plumbing or lead lined ducts were used to build homes decades ago, and natural refrigerators in the summer were also lead lined and have been banned for years, with plastic or other materials instead.
Many chemicals may degrade to harmless end compounds after a period of residence in the environment, but lead can no longer degrade and remains available once discharged into the environment for a long period of time. Lead has been classified as a strong pollutant because of its long-term persistence in the environment and its strong potential toxicity to many living tissues.
Stomachache, headache, tremor, and a decrease in the number of nervous dysphoric synapses, in the most severe cases, may be unconscious until death. At very low concentrations, the chronic long-term health effects of lead manifest as: affecting the brain and nervous system. Scientists have found that: even if the concentration of lead in blood samples of urban children is kept at an acceptable level, the blood samples still obviously affect the intelligence development and the performance behavior of the children. Only by reducing the level of lead in the environment can we ensure that the total amount of lead ingested by people is reduced.
The acquisition and utilization of energy are the subject of the invariance of human beings, and the transformation from the traditional fossil fuel to new energy such as wind energy, tide, nuclear energy, solar energy and the like, particularly the vigorous development of the photovoltaic industry represented by silicon-based solar cells enables people to see the infinite potential of the new energy to comprehensively replace the fossil energy. However, lead, which is a heavy metal, in the solar cell sheet cannot be degraded, maintains its usability for a long time once discharged into the environment, and has strong latent toxicity to many living tissues. In the production process of the battery piece, the lead content is not monitored from the purification, ingot casting and slicing of the silicon material to the texturing, diffusion, etching, PE, printing and other links of the battery piece.
Therefore, it is necessary to provide a method for detecting the lead content in the battery piece.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for detecting the lead content, which removes the interference of elements such as silicon, silver, aluminum and the like in a battery piece in a ball-milling reaction mode to remove, concentrate and purify the target lead element, and completes the accurate measurement of the lead content in the battery piece by controlling the process conditions in the detection method.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a method for detecting the lead content, which comprises the following steps:
(1) Performing first ball milling on a sample to be detected in an organic solvent to obtain a prefabricated product A;
(2) Performing secondary ball milling on the prefabricated product A obtained in the step (1) under the action of alkali and an organic solvent to obtain a prefabricated product B;
(3) Performing third ball milling on the prefabricated product B obtained in the step (2) under the action of dilute nitric acid and an organic solvent to obtain a prefabricated product C;
(4) Performing fourth ball milling on the prefabricated product C obtained in the step (3) under the action of concentrated sulfuric acid to obtain a prefabricated product D;
(5) And (4) testing the content of the lead in the preform D obtained in the step (4) by adopting a spectrophotometry method, so as to calculate the content of the lead in the sample to be tested.
In the invention, the interference of elements such as silicon, silver, aluminum and the like in the battery piece is removed in a wet ball milling reaction mode, the impurity removal, concentration and purification of the target lead element are achieved, and the accurate measurement of the lead content in the battery piece is completed by controlling the process conditions in the detection method.
In the invention, the step (1) aims at crushing a sample to be detected, the step (2) is used for removing silicon and aluminum in the sample to be detected, the step (3) is used for removing silver in the sample to be detected, the step (4) is used for converting lead elements to be detected into lead ions, and in the ball milling process of the step (4), an organic solvent is not required to be additionally added, so that the phenomenon that the concentrated sulfuric acid is diluted by the organic solvent to influence the reaction is avoided; and (5) converting the content of the lead ions in the solution into the content of lead in the sample to be detected by detecting the content of the lead ions in the solution.
In the invention, the sample to be detected in the step (1) is a battery piece.
In the present invention, the amount of the organic solvent added in step (1) is 5 to 20mL, for example, 5mL, 6mL, 7mL, 8mL, 9mL, 10mL, 11mL, 12mL, 13mL, 14mL, 15mL, 16mL, 17mL, 18mL, 19mL, 20mL, or the like, based on 1g of the sample to be tested.
In the present invention, the organic solvent in step (1) is a polyhydric alcohol, preferably any one of pentaerythritol, sorbitol or polyvinyl alcohol, or a combination of at least two thereof.
In the present invention, the addition amount of the first ball-milling ball material in the step (1) is 15 to 30g, for example, 15g, 17g, 20g, 22g, 25g, 27g, 30g, etc., based on 1g of the sample to be tested.
In the invention, the sample to be detected can be controlled to be fully ground by controlling the mass ratio of the sample to be detected and the ball material for the first ball milling.
In the present invention, the first ball-milling ball material in step (1) includes 5 to 20% (e.g., 5%, 7%, 10%, 12%, 15%, 17%, 20%, etc.) of small balls, 30 to 60% (e.g., 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, etc.) of medium balls, and 30 to 65% (e.g., 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, 62%, 65%, etc.) of large balls in mass fraction.
In the invention, the mass ratio of the big balls, the middle balls and the small balls in the ball material is controlled within a proper range, wherein the big balls have larger mass and the collision energy of the two balls is higher, thereby being more beneficial to the granulation of solid substances, and simultaneously, the particle size of the crushed object is not too small.
In the present invention, the small spheres have a particle size of 2 to 5mm (e.g., 2mm, 3mm, 4mm, 5mm, etc.), the medium spheres have a particle size of 5 to 15mm (e.g., 5.1mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, etc., excluding 5 mm), and the large spheres have a particle size of 15 to 25mm (e.g., 15.1mm, 16mm, 17mm, 18mm, 19mm, 20mm, 21mm, 22mm, 23mm, 24mm, 25mm, etc., excluding 15 mm).
In the present invention, the first ball milling in step (1) is performed at a rate of 300-800r/min, such as 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, etc. If the first ball milling speed is too slow, the ball kinetic energy is insufficient, and the crushing effect is poor; if the first ball milling rate is too fast, the large balls may be damaged.
In the present invention, the time of the first ball milling in step (1) is 0.5-5h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc. If the time for the first ball milling is too short, the ball milling effect is influenced; if the time of the first ball milling is too long, the ball milling effect is not greatly influenced.
In the invention, the ball mill for the first ball milling in the step (1) is a star ball mill.
In the invention, the step (1) further comprises the steps of performing solid-liquid separation, cleaning and drying on the ball-milled material obtained by the first ball milling.
In the present invention, the solid-liquid separation method is negative pressure filtration.
In the present invention, the cleaning solvent includes any one of ethanol, diethyl ether, methyl carbonate or ethyl acetate, or a combination of at least two thereof.
In the present invention, the drying temperature is 20 to 45 ℃, for example, 20 ℃, 22 ℃, 25 ℃, 27 ℃, 30 ℃, 32 ℃, 35 ℃, 37 ℃, 40 ℃, 42 ℃, 45 ℃ and the like.
In the present invention, the amount of the base added in step (2) is 5 to 10g (e.g., 5g, 6g, 7g, 8g, 9g, 10 g) based on 1g of the amount of the sample to be tested, and the volume of the organic solvent added is 10 to 20mL (e.g., 10mL, 11mL, 12mL, 13mL, 14mL, 15mL, 16mL, 17mL, 18mL, 19mL, 20mL, etc.).
In the present invention, the alkali in the step (2) comprises sodium hydroxide and/or potassium hydroxide.
In the present invention, the organic solvent of step (2) comprises an organic base and/or an organic ether.
In the present invention, the addition amount of the second ball-milling ball material in the step (2) is 5 to 50g, for example, 5g, 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g, 50g, etc., based on 1g of the addition amount of the sample to be measured. When the ratio of the addition amount of the sample to be tested to the addition amount of the ball material for the second ball milling is not in the range defined by the invention, incomplete reaction or ball damage is easy to form.
In the present invention, the second ball milling ball material in step (2) includes, by mass, 15 to 25% (e.g., 15%, 17%, 20%, 22%, 25%, etc.) of small balls, 45 to 65% (e.g., 45%, 47%, 50%, 52%, 55%, 57%, 60%, 62%, 65%, etc.) of medium balls, and 10 to 40% (e.g., 10%, 12%, 15%, 18%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, etc.) of large balls. When the composition of the ball material for the second ball milling is not within the range defined by the invention, the particle size after ball milling is easy to be too large or too small.
According to the invention, the grinding material for the second ball milling is regulated and controlled, so that the particle size distribution of the ball-milled sample is uniform.
In the present invention, the small spheres have a particle size of 2 to 5mm (e.g., 2mm, 3mm, 4mm, 5mm, etc.), the medium spheres have a particle size of 5 to 15mm (e.g., 5.1mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, etc., excluding 5 mm), and the large spheres have a particle size of 15 to 25mm (e.g., 15.1mm, 16mm, 17mm, 18mm, 19mm, 20mm, 21mm, 22mm, 23mm, 24mm, 25mm, etc., excluding 15 mm).
In the present invention, the second ball milling in step (2) is performed at a rate of 300-800r/min, such as 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, etc.
In the present invention, the time of the second ball milling in the step (2) is 2 to 6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc.
In the invention, the ball mill for the second ball milling in the step (2) is a pressure-relief ball mill.
The ball mill for the second ball milling in the invention is a pressure relief ball mill, which is used for preventing the explosion condition, because the silicon in the battery piece can react with alkali to generate hydrogen.
In the present invention, the volume of the diluted nitric acid added in step (3) is 3 to 10mL (e.g., 3mL, 4mL, 5mL, 6mL, 7mL, 8mL, 9mL, 10mL, etc.) and the amount of the organic solvent added is 5 to 20mL (e.g., 5mL, 6mL, 7mL, 8mL, 9mL, 10mL, 11mL, 12mL, 13mL, 14mL, 15mL, 16mL, 17mL, 18mL, 19mL, 20mL, etc.) based on 1g of the sample to be tested.
In the present invention, the concentration of the dilute nitric acid in the step (3) is 3-8%, such as 3%, 4%, 5%, 6%, 7%, 8%, etc.
In the present invention, the organic solvent in step (3) includes any one of ethanol, diethyl ether or methyl carbonate or a combination of at least two thereof.
In the present invention, the addition amount of the third ball-milling ball material in the step (3) is 5 to 50g, for example, 5g, 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g, 50g, etc., based on 1g of the addition amount of the sample to be tested. When the addition amount of the sample to be tested and the mass ratio of the ball material for the third ball milling are not in the range defined by the invention, the reaction rate is too slow or the ball is damaged.
In the present invention, the third ball mill ball material in step (3) includes 50 to 70% (e.g., 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, etc.) of small balls, 15 to 30% (e.g., 15%, 17%, 20%, 22%, 25%, 27%, 30%, etc.) of medium balls, and 5 to 20% (e.g., 5%, 7%, 10%, 12%, 15%, 17%, 20%, etc.) of large balls by mass fraction. When the composition of the ball for the third ball milling is out of the range defined in the present invention, the particle diameter is too small or too large to cause waste of the reaction material or incomplete reaction.
The composition of the ball material for the third ball milling is controlled in the invention to remove silver particles in the solid.
In the present invention, the small spheres have a particle size of 2 to 5mm (e.g., 2mm, 3mm, 4mm, 5mm, etc.), the medium spheres have a particle size of 5 to 15mm (e.g., 5.1mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, etc., excluding 5 mm), and the large spheres have a particle size of 15 to 25mm (e.g., 15.1mm, 16mm, 17mm, 18mm, 19mm, 20mm, 21mm, 22mm, 23mm, 24mm, 25mm, etc., excluding 15 mm).
In the present invention, the third ball milling in step (3) is performed at a rate of 500-1000r/min, such as 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, etc. In the invention, the third ball milling speed is too slow, which can cause incomplete reaction; when the ball milling speed is too fast, the effect on the ball milling result is not great.
In the present invention, the time of the third ball milling in step (3) is 2 to 6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc. When the time of the third ball milling is too short, incomplete reaction can be caused; if the time is too long, the influence on the ball milling result is not great.
In the present invention, the ball mill for the third ball milling in step (3) is a star ball mill.
In the invention, the step (3) further comprises cleaning and drying the ball-milled material obtained after the third ball milling.
In the present invention, the volume of the concentrated sulfuric acid added in step (4) is 5 to 10mL, for example, 5mL, 6mL, 7mL, 8mL, 9mL, 10mL, etc., based on 1g of the sample to be tested.
In the invention, the concentration of the concentrated sulfuric acid in the step (4) is 96%.
In the present invention, the amount of the fourth ball-milling material in the step (4) is 5 to 50g, for example, 5g, 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g, 50g, etc., based on 1g of the sample to be tested. When the ratio of the addition amount of the sample to be tested to the addition amount of the ball material for the fourth ball milling is not within the range defined by the invention, the reaction rate is too slow or the ball is damaged.
In the present invention, the fourth ball mill ball material in step (4) includes 60 to 80% (e.g., 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, etc.) of small balls, 10 to 40% (e.g., 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, etc.) of medium balls, and 0 to 10% (e.g., 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.) of large balls in mass fraction. When the composition of the ball for the fourth ball milling is out of the range defined in the present invention, the particle diameter is too small or too large to cause waste of the reaction material or incomplete reaction.
The composition of the ball material for the fourth ball milling is controlled in the invention to ensure that the particle size of the particles obtained after ball milling is less than 5 μm.
In the present invention, the fourth ball milling in step (4) is performed at a rate of 500-1000r/min, such as 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, etc.
In the present invention, the time of the fourth ball milling in the step (4) is 2 to 6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc.
In the present invention, the ball mill for the fourth ball milling in the step (4) is a vibration ball mill. If the ball mill for the fourth ball milling is a common star ball mill, the particle size diameter is too large, which is not beneficial to lead element concentration.
In the present invention, the step (5) further comprises diluting the preform D before the spectrophotometric test is performed.
In the present invention, the diluting solvent is water.
In the present invention, the addition amount ratio of the preform D and the diluting solvent is 1 (5-20), such as 1.
In the invention, the spectrophotometry in the step (5) is a dual-wavelength spectrophotometry.
In the present invention, the wavelength for the spectrophotometry in the step (5) is 300 to 900nm, for example, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, etc.
As a preferred embodiment of the present invention, the method for detecting lead includes:
(1) Adding a sample to be detected and first ball-milling ball materials (comprising small balls with the mass fraction of 5-20%, medium balls with the mass fraction of 30-60% and large balls with the mass fraction of 30-65%) into a star-type ball mill, adding an organic solvent (the addition of the sample to be detected is 1g, the addition of the first ball-milling ball materials is 15-30g, and the addition of the organic solvent is 5-10 mL), carrying out ball milling for 0.5-5h under the condition that the ball-milling speed is 300-800r/min to obtain a ball-milled object, then carrying out negative pressure filtration and cleaning on the obtained ball-milled object, and drying at the temperature of 20-45 ℃ to obtain a prefabricated product A;
(2) Performing secondary ball milling on the preform A obtained in the step (1) in a pressure-release ball mill under the action of alkali and an organic solvent (the addition of the sample to be tested is 1g, the addition of the alkali is 5-10g, and the addition of the organic solvent is 10-20 mL) (the addition of the sample to be tested is 1g, the addition of a ball material for the secondary ball milling is 5-50g, and the ball material for the secondary ball milling comprises 15-25% of small balls, 45-65% of medium balls and 10-40% of large balls by mass fraction), and performing ball milling for 2-6h under the condition that the ball milling speed is 300-800r/min to obtain a preform B;
(3) Carrying out third ball milling on the prefabricated product B obtained in the step (2) in a star ball mill under the action of dilute nitric acid and an organic solvent (the addition of a sample to be tested is 1g, the addition of the dilute nitric acid is 3-10mL, and the addition volume of the organic solvent is 5-20 mL) (the addition of the sample to be tested is 1g, the addition of ball materials for the third ball milling is 5-50g, the ball materials for the third ball milling comprise 50-70% of small balls, 15-30% of medium balls and 5-20% of large balls in mass fraction), carrying out ball milling for 5-6h under the condition that the ball milling speed is 500-1000r/min, and then carrying out cleaning and drying to obtain a prefabricated product C;
(4) Performing fourth ball milling on the prefabricated product C obtained in the step (3) in a vibration type ball mill under the action of concentrated sulfuric acid (the adding amount of a sample to be tested is 1g, and the adding volume of the concentrated sulfuric acid is 5-10 mL), wherein the adding amount of the sample to be tested is 1g, the adding amount of ball materials for the fourth ball milling is 5-50g, the ball materials for the fourth ball milling comprise 60-80% of small balls, 10-40% of medium balls and 0-10% of large balls in mass fraction, and performing ball milling for 2-6h under the condition that the ball milling speed is 500-1000r/min to obtain a prefabricated product D;
(5) And (5) diluting the preform D obtained in the step (4) with water according to the mass ratio of 1 (5-20) to obtain a diluent, and testing the obtained diluent according to a dual-wavelength spectrophotometry method so as to calculate the content of lead in the sample to be tested.
The lead content detection method of the second object of the invention is applied to quality sampling inspection or environmental evaluation of battery pieces.
Compared with the prior art, the invention has the following beneficial effects:
the invention removes the interference of elements such as silicon, silver, aluminum and the like in the battery piece in a ball-milling reaction mode, achieves the purposes of impurity removal, concentration and purification of the target lead element, and completes the accurate measurement of the lead content in the battery piece (the error is less than 10%) by controlling the process conditions in the detection method.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a method for detecting lead content, which comprises the following steps:
(1) Weighing a battery piece, vertically cutting the battery piece along a cross center line, taking one fourth of the battery piece as a sample, and weighing the battery piece with the mass of 4g;
(2) Grinding and crushing the sampled product, adding ball-milled agate balls (the adopted agate balls comprise 10% of small balls, 40% of medium balls and 50% of large balls) according to the mass ratio of 1;
(3) Adding the prefabricated product A obtained in the step (2) into 30g of ball-milled agate balls (the adopted agate balls comprise small balls with the mass fraction of 20%, medium balls with the mass fraction of 55% and large balls with the mass fraction of 25%), and carrying out ball milling in a pressure-release ball mill under the action of 30g of sodium hydroxide and 50mL of ethanol, wherein the ball milling speed is 500r/min, and the ball milling time is 5h, so as to obtain a prefabricated product B;
(4) Adding the prefabricated product B obtained in the step (3) into 30g of ball-milled agate balls (the adopted agate balls comprise small balls with the mass fraction of 60%, middle balls with the mass fraction of 25% and large balls with the mass fraction of 15%), carrying out ball milling in a star-type ball mill under the action of 30mL of 5% dilute nitric acid and 10mL of ethanol, wherein the ball milling speed is 800r/min, the ball milling time is 6h, and then cleaning and drying to obtain a prefabricated product C;
(5) Adding the prefabricated product C obtained in the step (4) into 30g of ball-milled agate balls (the adopted agate balls comprise small balls with the mass fraction of 70%, medium balls with the mass fraction of 25% and large balls with the mass fraction of 5%), and carrying out ball milling in a vibration type ball mill under the action of 20mL of concentrated sulfuric acid with the concentration of 96%, wherein the ball milling speed is 800r/min, and the ball milling time is 5h, so as to obtain a prefabricated product D;
(6) Diluting the preform D obtained in the step (5) with water according to a mass ratio of 1;
(7) Preparing lead ion standard solutions with concentration gradients of 0.1mol/L, 0.3mol/L and 0.5mol/L respectively, testing the absorbance of the lead ion standard solution at the wavelength of 300-900nm by using a spectrophotometer (model 722G, manufacturer Trouce), drawing a standard curve according to the concentration of the lead ion standard solution and the absorbance corresponding to the lead ion standard solution, and quantifying the concentration of the lead ions in the diluent obtained in the step (6) according to the standard curve.
Making a standard curve according to the absorbance and the concentration to obtain a regression equation y =0.4102x-4.3671
Obtaining a linear correlation coefficient (R) from the regression equation 2 ) A value of 0.9725 indicates that the standard curve is well linear.
And (4) testing the concentration of the diluent in the step (6) by taking the standard curve as a basis, wherein the concentration of the lead ions in the diluent is 2.42 multiplied by 10 after the test -4 And mol/L is calculated according to the formula M =4 xM xc xV, wherein M is the relative atomic mass of the lead and is 207, c represents the concentration of lead ions in the diluent, V represents the volume of the diluent and is 1100mL, and the content of the lead in the battery piece is 0.22mg through calculation.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.26mg, and the amount of the lead oxide added is 0.24mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content and the lead content added in the battery manufacturing process in the embodiment is 8.3 percent, and the test method is proved to be accurate and reliable.
Example 2
The embodiment provides a method for detecting lead content, which comprises the following steps:
(1) Weighing a battery piece, vertically cutting the battery piece along the central line of the cross, taking one fourth of the battery piece as a sample, and weighing the battery piece with the mass of 4g;
(2) Grinding and crushing the sampled product, adding ball-milled agate balls (the adopted agate balls comprise 5% of small balls, 30% of medium balls and 65% of large balls) according to the mass ratio of 1;
(3) Adding the prefabricated product A obtained in the step (2) into 50g of ball-milled agate balls (the adopted agate balls comprise 15% of small balls, 45% of medium balls and 40% of large balls in mass fraction), and carrying out ball milling in a pressure-release ball mill under the action of 5g of sodium hydroxide and 10mL of ethanol, wherein the ball-milling speed is 300r/min, and the ball-milling time is 6h to obtain a prefabricated product B;
(4) Adding the prefabricated product B obtained in the step (3) into 50g of ball-milled agate balls (the adopted agate balls comprise 50% of small balls, 30% of medium balls and 20% of large balls in mass fraction), carrying out ball milling in a star-type ball mill under the action of 3mL of 5% dilute nitric acid and 20mL of ethanol, wherein the ball milling speed is 500r/min, the ball milling time is 6h, and then cleaning and drying to obtain a prefabricated product C;
(5) Adding the prefabricated product C obtained in the step (4) into 50g of ball-milling agate balls (the adopted agate balls comprise small balls with the mass fraction of 60% and medium balls with the mass fraction of 40%), and carrying out ball milling in a vibration type ball mill under the action of 5mL of 96% concentrated sulfuric acid, wherein the ball-milling speed is 500r/min, and the ball-milling time is 6h, so as to obtain a prefabricated product D;
(6) Diluting the preform D obtained in the step (5) with water according to the mass ratio of 1;
(7) The concentration of lead ions in the dilution obtained in step (6) was quantified according to the standard curve prepared in example 1.
The concentration of the diluted solution obtained in the step (6) was measured based on the standard curve of example 1, and the concentration of lead ions in the diluted solution was measured to be 4.57 × 10 -4 mol/L according to as described inThe same calculation formula as in example 1 gave a lead content of 0.308mg in the battery sheet.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.32mg, and the amount of the lead oxide added is 0.297mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the embodiment and the lead content added in the battery manufacturing process is 3.5%, and the method for testing the lead content is proved to be accurate and reliable.
Example 3
The embodiment provides a method for detecting lead content, which comprises the following steps:
(1) Weighing a battery piece, vertically cutting the battery piece along the central line of the cross, taking one fourth of the battery piece as a sample, and weighing the battery piece with the mass of 4g;
(2) Grinding and crushing the sampled product, adding ball-milled agate balls (the adopted agate balls comprise 20% of small balls, 30% of medium balls and 50% of large balls in mass fraction) according to the mass ratio of 1;
(3) Adding the prefabricated product A obtained in the step (2) into 5g of ball-milled agate balls (the adopted agate balls comprise 25% of small balls, 65% of medium balls and 10% of large balls in mass fraction), and carrying out ball milling in a pressure-release ball mill under the action of 10g of sodium hydroxide and 20mL of ethanol, wherein the ball-milling speed is 800r/min, and the ball-milling time is 2h to obtain a prefabricated product B;
(4) Adding the prefabricated product B obtained in the step (3) into 5g of ball-milled agate balls (the adopted agate balls comprise small balls with the mass fraction of 70%, medium balls with the mass fraction of 15% and large balls with the mass fraction of 15%), carrying out ball milling in a star-type ball mill under the action of 10mL of 5% dilute nitric acid and 5mL of ethanol, wherein the ball milling speed is 1000r/min, the ball milling time is 5h, and then cleaning and drying to obtain a prefabricated product C;
(5) Adding the prefabricated product C obtained in the step (4) into 5g of ball-milled agate balls (the adopted agate balls comprise small balls with the mass fraction of 80%, middle balls with the mass fraction of 10% and large balls with the mass fraction of 10%), and carrying out ball milling in a vibration type ball mill under the action of 10mL of concentrated sulfuric acid with the concentration of 96%, wherein the ball milling speed is 1000r/min, and the ball milling time is 2h, so as to obtain a prefabricated product D;
(6) Diluting the preform D obtained in the step (5) with water according to a mass ratio of 1;
(7) The concentration of lead ions in the dilution obtained in step (6) was quantified according to the standard curve prepared in example 1.
The concentration of the diluted solution obtained in the step (6) was measured based on the standard curve of example 1, and the concentration of lead ions in the diluted solution was measured to be 1.28X 10 -4 mol/L was calculated according to the same calculation formula as in example 1 to obtain a lead content of 0.270mg in the battery piece.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added into the cell sample to be tested is 0.270mg, and the amount of the lead oxide added is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the embodiment and the lead content added in the battery manufacturing process is 7.04%, and the method for testing the lead content is proved to be accurate and reliable.
Comparative example 1
The difference from example 1 is only that the first ball milling speed is 100r/min, and the rest of the detection method is the same as example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 2.31 × 10 -4 mol/L, calculated according to the same calculation formula as example 1, gave a lead content in the battery piece of 0.20mg.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 20.3%, which shows that when the first ball milling speed is too low, the accuracy of the test result is greatly influenced.
Comparative example 2
The difference from the example 1 is only that the ratio of the addition amount of the sample to be tested to the addition amount of the ball material for the second ball milling is 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 1.91 × 10 -4 mol/L was calculated according to the same calculation formula as in example 1 to obtain a lead content of 0.082mg in the battery plate.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount of the lead oxide added is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 67%, which shows that when the addition ratio of the sample to be tested and the ball material for secondary ball milling is not in the range limited by the invention, the relative error has a large influence on the accuracy of the test result.
Comparative example 3
The difference from example 1 is that the second ball-milling ball material comprises 10% of small balls, 80% of medium balls and 10% of large balls, and the rest of the detection method is the same as that of example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 1.01X 10 -4 mol/L was calculated according to the same calculation formula as in example 1 to obtain a lead content of 0.067mg in the battery piece.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 73.3%, which shows that when the composition of the ball material for secondary ball milling is not in the limited range of the invention, the accuracy of the test result is greatly influenced.
Comparative example 4
The difference from example 1 is only that the second ball milling speed is 100r/min, and the rest of the detection method is the same as that of example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 1.2 × 10 -4 mol/L, calculated according to the same calculation formula as example 1, gave a lead content in the cell sheet of 0.078mg.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount of the lead oxide added is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the content of the lead added in the battery manufacturing process is 68.9%, which shows that when the speed of the second ball milling is too low, the accuracy of the test result is greatly influenced.
Comparative example 5
The method is different from that of example 1 only in that the ball mill for the second ball milling is a star ball mill, and the rest detection method is the same as that of example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 5.92X 10 -4 mol/L, calculated according to the same calculation formula as example 1, gave a lead content in the cell sheet of 0.317mg.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content and the lead content added in the battery manufacturing process in the comparative example is 26.3%, which shows that when the ball mill for the second ball milling is replaced by the conventional star-shaped ball mill, although the difference of the test results is not greatly influenced, the pressure in the ball mill is overlarge due to the fact that silicon wafers can react with alkali to generate a large amount of hydrogen in the second ball milling process, and certain potential safety hazards exist.
Comparative example 6
The difference from the example 1 is only that the mass ratio of the sample to be detected to the ball material for the third ball milling is 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 4.92 × 10 -4 mol/L, calculated according to the same calculation formula as example 1, gave a lead content in the battery piece of 0.295mg.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 17.5%, which shows that the mass ratio of the sample to be detected and the ball material for the third ball milling is not in the range defined by the invention, and the relative error has great influence on the test result.
Comparative example 7
The difference from example 1 is that the third ball mill ball material includes 40% of small balls, 50% of medium balls and 10% of small balls, and the rest of the detection method is the same as example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 2.92X 10 -4 mol/L was calculated according to the same calculation formula as in example 1 to obtain a lead content of 0.189mg in the battery piece.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 24.7%, which shows that when the composition of the ball material for the third ball milling is not in the range defined by the invention, the test result is greatly influenced.
Comparative example 8
The difference from example 1 is only that the third ball milling speed is 300r/min, and the rest of the detection method is the same as that of example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 2.80X 10 -4 mol/L was calculated according to the same calculation formula as in example 1 to obtain a lead content of 0.178mg in the battery piece.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 29.0%, which shows that when the ball milling speed of the third ball milling is too low, the test result is greatly influenced.
Comparative example 9
The difference from the example 1 is only that the mass ratio of the sample to be detected to the ball material for the fourth ball milling is 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 3.31X 10 -4 mol/L, calculated according to the same calculation formula as example 1, gave a lead content in the battery piece of 0.216mg.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount of the lead oxide added is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 13.9%, which shows that when the mass ratio of the sample to be detected and the ball material for the fourth ball milling is not in the range defined by the invention, the test result is greatly influenced.
Comparative example 10
The difference from example 1 is that the fourth ball mill ball material comprises 50% of small balls and 50% of medium balls, and the rest of the detection method is the same as that of example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 7.31X 10 -4 mol/L was calculated according to the same calculation formula as in example 1 to obtain a lead content of 0.49mg in the battery piece.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount of the lead oxide added is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 95.2%, which shows that when the composition of the ball material for the fourth ball milling is not in the range defined by the invention, the relative error has a great influence on the test result.
Comparative example 11
The difference from example 1 is only that the fourth ball milling speed is 300r/min, and the rest of the detection method is the same as that of example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 4.01X 10 -4 mol/L, calculated according to the same calculation formula as example 1, gave a lead content of 0.221mg in the battery piece.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount of the lead oxide added is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 12%, which shows that when the speed of the fourth ball milling is too low, the test result is greatly influenced.
Comparative example 12
The difference from example 1 is only that the ball mill for the fourth ball milling is a star ball mill, and the rest of the detection method is the same as that of example 1.
The concentration of the diluted solution was measured based on the standard curve in example 1, and the concentration of lead ions in the diluted solution was measured to be 3.47 × 10 -4 mol/L was calculated according to the same calculation formula as in example 1 to obtain a lead content of 0.285mg in the battery piece.
The lead in the cell sample to be tested is mainly derived from lead oxide added into the slurry glass powder, the amount of the lead oxide added in the cell sample to be tested is 0.27mg, and the amount is 0.251mg in terms of the addition amount of lead element.
The relative error between the detection result of the lead content in the comparative example and the lead content added in the battery manufacturing process is 13.5%, which shows that when the conventional star-type ball mill is used for the fourth ball milling, the test result is greatly influenced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The method for detecting the lead content is characterized by comprising the following steps of:
(1) Carrying out first ball milling on a sample to be detected in a first organic solvent to obtain a prefabricated product A;
(2) Performing secondary ball milling on the prefabricated product A obtained in the step (1) under the action of alkali and a second organic solvent to obtain a prefabricated product B;
(3) Performing third ball milling on the prefabricated product B obtained in the step (2) under the action of dilute nitric acid and a third organic solvent to obtain a prefabricated product C;
(4) Performing fourth ball milling on the prefabricated product C obtained in the step (3) under the action of concentrated sulfuric acid to obtain a prefabricated product D;
(5) Testing the content of lead in the preform D obtained in the step (4) by adopting a spectrophotometry method, so as to calculate the content of lead in the sample to be tested;
the first organic solvent in the step (1) is polyalcohol;
the second organic solvent of step (2) comprises an organic base and/or an organic ether;
the third organic solvent in the step (3) comprises any one or a combination of at least two of ethanol, diethyl ether or methyl carbonate.
2. The method for detecting lead content according to claim 1, wherein the sample to be detected in step (1) is a battery piece;
the step (1) also comprises the step of grinding and crushing the sample to be detected before the first ball milling;
the adding amount of the first organic solvent in the step (1) is 3-10mL calculated by the adding amount of the sample to be detected as 1 g;
the first organic solvent in the step (1) is any one or the combination of at least two of pentaerythritol, sorbitol or polyvinyl alcohol;
the adding amount of the ball material used in the first ball milling in the step (1) is 15-30g calculated by 1g of the adding amount of the sample to be detected;
ball materials adopted by the first ball milling in the step (1) comprise 5-20% of small balls, 30-60% of medium balls and 30-65% of large balls in percentage by mass;
the particle size of the small balls is 2-5mm, the particle size of the medium balls is 5-15mm, and the particle size of the large balls is 15-25 mm;
the speed of the first ball milling in the step (1) is 300-800 r/min;
the time of the first ball milling in the step (1) is 0.5-5 h;
the ball mill adopted in the first ball milling in the step (1) is a star ball mill.
3. The method for detecting the content of lead according to claim 1, wherein the step (1) further comprises performing solid-liquid separation, cleaning and drying on a ball-milled material obtained by the first ball milling;
the solid-liquid separation mode is negative pressure filtration;
the solvent adopted for cleaning comprises any one or the combination of at least two of ethanol, diethyl ether, methyl carbonate or ethyl acetate;
the drying temperature is 20-45 ℃.
4. The method for detecting the lead content according to claim 1, wherein the addition amount of the alkali in the step (2) is 5 to 10g, and the addition volume of the second organic solvent is 10 to 20mL, based on 1g of the addition amount of the sample to be detected;
the alkali in the step (2) comprises sodium hydroxide and/or potassium hydroxide;
counting the addition amount of the sample to be detected as 1g, wherein the addition amount of the ball material adopted in the second ball milling in the step (2) is 5-50 g;
ball materials adopted by the second ball milling in the step (2) comprise 15-25% of small balls, 45-65% of medium balls and 10-40% of large balls in mass fraction;
the particle size of the small balls is 2-5mm, the particle size of the medium balls is 5-15mm, and the particle size of the large balls is 15-25 mm;
the speed of the second ball milling in the step (2) is 300-800 r/min;
the time of the second ball milling in the step (2) is 2-6 h;
and (3) the ball mill adopted in the second ball milling in the step (2) is a pressure-relief ball mill.
5. The method for detecting the lead content according to claim 1, wherein the addition volume of the dilute nitric acid in the step (3) is 3-10mL, and the addition amount of the third organic solvent is 5-20mL, based on 1g of the addition amount of the sample to be detected;
the concentration of the dilute nitric acid in the step (3) is 3-8%;
the adding amount of the ball material adopted by the third ball milling in the step (3) is 5-50g by taking the adding amount of the sample to be detected as 1 g;
ball materials adopted by the third ball milling in the step (3) comprise 50-70% of small balls, 15-30% of medium balls and 5-20% of large balls in mass fraction;
the particle size of the small balls is 2-5mm, the particle size of the medium balls is 5-15mm, and the particle size of the large balls is 15-25 mm;
the speed of the third ball milling in the step (3) is 500-1000 r/min;
the time of the third ball milling in the step (3) is 2-6 h;
the ball mill adopted in the third ball milling in the step (3) is a star ball mill;
and the step (3) also comprises the step of cleaning and drying the ball-milled material obtained after the third ball milling.
6. The method for detecting the lead content according to claim 1, wherein the volume of the concentrated sulfuric acid added in the step (4) is 5-10mL based on 1g of the sample to be detected;
the concentration of the concentrated sulfuric acid in the step (4) is 96%;
the adding amount of the ball materials used in the fourth ball milling in the step (4) is 5-50g calculated by 1g of the adding amount of the sample to be tested;
ball materials adopted by the fourth ball milling in the step (4) comprise 60-80% of small balls, 10-40% of medium balls and 0-10% of large balls in percentage by mass;
the speed of the fourth ball milling in the step (4) is 500-1000 r/min;
the time of the fourth ball milling in the step (4) is 2-6 h;
and (4) adopting a vibration ball mill as the ball mill for the fourth ball milling.
7. The method for detecting lead content according to claim 1, wherein the step (5) further comprises diluting the preform D before the spectrophotometric test;
the dilution adopts water as a solvent;
the addition ratio of the preform D to the solvent for dilution is 1 (5-20).
8. The method for detecting lead content according to claim 1, wherein the spectrophotometry of step (5) is a two-wavelength spectrophotometry;
the wavelength of the spectrophotometry in the step (5) is 300-900 nm.
9. The method for detecting lead content according to claim 1, characterized by comprising the steps of:
(1) Adding a sample to be detected and ball materials adopted for first ball milling into a star-type ball mill, adding a first organic solvent, carrying out ball milling for 0.5-5h under the condition that the ball milling speed is 300-800r/min to obtain a ball milling object, then carrying out negative pressure filtration and cleaning on the obtained ball milling object, and drying at 20-45 ℃ to obtain a prefabricated product A;
wherein, the ball material adopted by the first ball milling comprises 5 to 20 mass percent of small balls, 30 to 60 mass percent of medium balls and 30 to 65 mass percent of large balls;
the adding amount of the ball material used for the first ball milling is 15-30g, and the adding amount of the first organic solvent is 5-10mL, wherein the adding amount of the sample to be detected is 1 g;
(2) Performing secondary ball milling on the prefabricated product A obtained in the step (1) in a pressure-release ball mill under the action of alkali and a second organic solvent, and performing ball milling for 2-6h under the condition that the ball milling speed is 300-800r/min to obtain a prefabricated product B;
wherein the addition amount of the alkali is 5-10g and the addition amount of the second organic solvent is 10-20mL based on 1g of the addition amount of the sample to be detected;
the adding amount of the sample to be detected is 1g, the adding amount of the ball materials used in the second ball milling is 5-50g, and the ball materials used in the second ball milling comprise 15-25% of small balls, 45-65% of medium balls and 10-40% of large balls in mass fraction;
(3) Performing third ball milling on the prefabricated product B obtained in the step (2) in a star ball mill under the action of dilute nitric acid and a third organic solvent, performing ball milling for 5-6h under the condition that the ball milling speed is 500-1000r/min, and then cleaning and drying to obtain a prefabricated product C;
wherein the addition amount of the dilute nitric acid is 3-10mL, and the addition volume of the third organic solvent is 5-20mL, based on 1g of the addition amount of the sample to be detected;
the adding amount of the ball materials used for the third ball milling is 5-50g, and the ball materials used for the third ball milling comprise 50-70% of small balls, 15-30% of medium balls and 5-20% of large balls in mass fraction, wherein the adding amount of the sample to be tested is 1 g;
(4) Performing fourth ball milling on the prefabricated product C obtained in the step (3) in a vibration type ball mill under the action of concentrated sulfuric acid, and performing ball milling for 2-6h under the condition that the ball milling speed is 500-1000r/min to obtain a prefabricated product D;
wherein the adding volume of concentrated sulfuric acid is 5-10mL, wherein the adding amount of a sample to be detected is 1 g;
the adding amount of the ball materials used in the fourth ball milling is 5-50g, and the ball materials used in the fourth ball milling comprise 60-80% of small balls, 10-40% of medium balls and 0-10% of large balls in mass fraction, wherein the adding amount of the sample to be tested is 1 g;
(5) And (5) diluting the preform D obtained in the step (4) with water according to the mass ratio of 1 (5-20) to obtain a diluent, and testing the obtained diluent according to a dual-wavelength spectrophotometry method so as to calculate the content of lead in the sample to be tested.
10. Use of the method for detecting lead content according to any one of claims 1 to 9 in battery piece quality spot check or environmental assessment.
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| CN102560535A (en) * | 2012-01-13 | 2012-07-11 | 河南科技大学 | Method for recovering lead in waste lead-acid storage battery filler by using wet process |
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| CN104697983A (en) * | 2015-03-18 | 2015-06-10 | 河北金木药业集团有限公司 | Method of detecting heavy metal lead, cadmium, arsenic and copper in TCM (Traditional Chinese Medicine) tablet |
| CN107302118A (en) * | 2016-04-15 | 2017-10-27 | 北京化工大学 | A kind of lead oxide that reclaims is as the high-performance lead-acid accumulator of active material |
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| CN102560535A (en) * | 2012-01-13 | 2012-07-11 | 河南科技大学 | Method for recovering lead in waste lead-acid storage battery filler by using wet process |
| CN103509949A (en) * | 2012-06-15 | 2014-01-15 | 杨春晓 | Methods and equipment for recovering waste diachylon by wet method and manufacturing electrode active material of high performance lead acid battery by wet method |
| CN104697983A (en) * | 2015-03-18 | 2015-06-10 | 河北金木药业集团有限公司 | Method of detecting heavy metal lead, cadmium, arsenic and copper in TCM (Traditional Chinese Medicine) tablet |
| CN107302118A (en) * | 2016-04-15 | 2017-10-27 | 北京化工大学 | A kind of lead oxide that reclaims is as the high-performance lead-acid accumulator of active material |
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