CN112129826A - Quantitative analysis method for SPS in electrolyte for anti-drawing copper foil - Google Patents
Quantitative analysis method for SPS in electrolyte for anti-drawing copper foil Download PDFInfo
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Abstract
The invention discloses a quantitative analysis method of SPS in electrolyte for anti-pulling copper foil, which comprises the steps of preparing copper sulfate detection matrix solution in a quantitative container, preparing SPS standard solution, adding an electrolyte sample of the SPS to be detected into a reaction tank containing the detection matrix solution, analyzing and recording the change of a voltammetry characteristic curve by using a cyclic voltammetry method, then adding the SPS standard solution into the reaction tank after the detection sample is added discontinuously, recording the cyclic voltammetry curve before and after the SPS standard solution is added every time, and calculating the concentration of the SPS in the electrolyte according to the deviation of the two. According to the quantitative analysis method for SPS in the electrolyte for the anti-tensile copper foil, disclosed by the invention, the interference of other additives in the electrolyte is eliminated by adding the components of the matrix solution, the SPS content in the electrolyte can be accurately detected, the regulation and control direction of a production process can be accurately guided, and a solid guarantee is provided for the production of the stable anti-tensile copper foil.
Description
Technical Field
The invention relates to the technical field of lithium electrolytic copper foil manufacturing, in particular to a quantitative analysis method for SPS in electrolyte for a tensile copper foil.
Background
With the vigorous development of the new energy automobile industry, the market demand for power batteries is always in a vigorous trend. As a negative electrode collector material of a power battery, the market demand of lithium electrolytic copper foil is greatly driven. Along with the increasing capacity of the domestic lithium-ion electro-copper foil in recent years, the market competition of the copper foil is more and more intense, and the high-end lithium-ion electro-copper foil product in the market is always in a state of beauty.
The non-pleating and continuous-carrying are the core competition points of the copper foil for the power battery and the most severe performance requirements of power battery enterprises on the copper foil. However, the lithium battery foils in the current market are mainly classified into common lithium battery foils with tensile strength from the viewpoint of tensile strength, the tensile strength is about 280-. Therefore, the research and development of the copper foil with moderate tensile strength and the process capable of better matching with the power battery become the problem which needs to be solved urgently at present.
In the electrolytic production process of the lithium-ion electrolytic copper foil, the additive is the key for regulating and controlling the surface properties of the copper foil and optimizing the physical properties. Through multiple tests, the content of the sodium polydithio-dipropyl sulfonate (SPS) in the additive plays an irreplaceable role in the high and low tensile strength and the stability of the copper foil with the intermediate tensile strength.
The tensile strength copper foil is an important material meeting the requirements of a specific power battery, and the tensile strength is between 350-400 MPa. The SPS plays a role in refining crystal grains and enhancing the bonding force among the crystal grains in the production process of the tensile strength resistant copper foil, and is one of the most important additive components for controlling the tensile strength of the electroplated copper foil. The low SPS content can cause the insufficient tensile strength of the copper foil, the high SPS content can cause the excessive tensile strength of the copper foil and the excessive surface tension, and the production process control is influenced. The level of control of the SPS content in the electrolyte determines the production level of the tensile strength copper foil.
Disclosure of Invention
In view of the above technical problems in the related art, the present invention provides a method for quantitatively analyzing SPS in an electrolyte for a stretch-proof copper foil, which can overcome the above disadvantages in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
a quantitative analysis method for SPS in electrolyte for anti-drawing copper foil comprises the following steps:
s1: preparing imitation electrolyte, adding an auxiliary solution into the imitation electrolyte to prepare a detection matrix solution, and adding SPS into the imitation electrolyte to prepare an SPS standard solution;
s2: taking the electrolyte for the medium tensile strength copper foil to be detected, and diluting the electrolyte in a certain proportion to be used as a sample to be detected;
s3: adding a detection matrix solution into a reaction tank of a three-electrode system, activating electrodes by using the three-electrode system, and analyzing and recording a voltammetry characteristic curve of the detection matrix solution as a basic curve after the curve is stable;
s4: adding a sample to be tested into a reaction tank, fully stirring, and recording a voltammetry characteristic curve of the sample by using a cyclic voltammetry method;
s5: adding the SPS standard solution into a reaction tank, fully stirring, recording a standard voltammetry characteristic curve by using a cyclic voltammetry method, and repeating the step;
s6: and analyzing the volt-ampere characteristic curve to obtain a sample fitting curve, and calculating the concentration of the SPS in the sample according to the sample fitting curve.
Further, the imitation electrolyte solution in the step S1 includes H2SO4And CuSO4The auxiliary solution comprises a displacement agent and a brightening agent.
Further, in the auxiliary solution, the displacement agent comprises a main displacement agent and an auxiliary displacement agent, the brightener comprises an auxiliary brightener, the concentration of the main displacement agent is 300-500mg/L, the concentration of the auxiliary displacement agent is 80-150mg/L, the concentration of the auxiliary brightener is 5-15mg/L, and the SPS concentration in the SPS standard solution is 20-150 mg/L.
Further, the volume of the detection matrix solution in the step S3 is 30-50 mL.
Further, the volume of the sample to be tested added in step S4 is 1-3 mL.
Further, the number of times of adding the SPS standard solution in the step S5 is 2-4.
Further, the SPS standard solution is added in a volume of 0.05-0.25mL in each step S5.
The quantitative analysis method aims at the fact that a plurality of groups of premixed liquid need to be prepared for verification according to the formula of each group of new additives of the tensile strength copper foil, and the deviation between the detection concentration and the prediction concentration of the premixed liquid is required to be less than 10%.
The abscissa of the sample fitting curve is the corrected concentration added by the SPS standard solution or the sample, the ordinate is the transferred electric quantity in the whole electrochemical process, the fitting mode is linear fitting, and the correction judgment coefficient R of each fitting curve is required2≥0.999。
The invention has the beneficial effects that: according to the quantitative analysis method for SPS in the electrolyte for the anti-tensile copper foil, disclosed by the invention, the interference of other additives in the electrolyte is eliminated by adding the components of the matrix solution, the SPS content in the electrolyte can be accurately detected, the regulation and control direction of a production process can be accurately guided, and a solid guarantee is provided for the production of the stable anti-tensile copper foil.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic diagram of a reaction tank of a three-electrode system according to an embodiment of the present invention;
FIG. 2 is a graph of the voltammetric curves of an SPS standard solution and a test sample according to an embodiment of the invention;
FIG. 3 is a graph of SPS concentration transition charge in accordance with an embodiment of the invention;
in the figure: 1. reaction tank, 2, working electrode, 3, reference electrode, 4, auxiliary electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The method for quantitatively analyzing the SPS in the electrolyte for the anti-pulling copper foil comprises the following steps of preparing an electrolyte in a quantitative container, preparing a copper sulfate detection matrix solution, preparing an SPS standard solution, adding an electrolyte sample to be detected into a reaction tank containing the detection matrix solution, analyzing and recording the change of a voltammetry characteristic curve by using a cyclic voltammetry method, discontinuously adding the SPS standard solution into the reaction tank after the detection sample is added, recording the cyclic voltammetry curve before and after the SPS standard solution is added every time, and calculating the concentration of the SPS in the electrolyte according to the deviation of the two steps:
firstly, preparing imitation electrolyte, wherein the imitation electrolyte comprises the constituents of the imitation electrolyte prepared according to the proportion of a workshop electrolyte process and corresponds to the concentration of an actual sample after dilution. Preparing an imitation electrolyte: 351.56g of copper sulfate pentahydrate powder and 120g of concentrated sulfuric acid were weighed and mixed with ultrapure water to prepare 2.5L of an imitation electrolyte, and then 1mL of 3% diluted hydrochloric acid was added.
And secondly, preparing a detection matrix solution, taking a 500mL volumetric flask, wetting and washing with an imitation electrolyte, adding 0.5mL auxiliary solution with the concentration of 10g/L, and fixing the volume to a scale mark with the imitation electrolyte to prepare the detection matrix solution.
And preparing the SPS standard solution again, taking a 100mL volumetric flask, wetting and washing with the imitation electrolyte, adding 0.25mL of SPS stock solution with the concentration of 10g/L, and fixing the volume to a scale mark with the imitation electrolyte to prepare the SPS standard solution with the concentration of 25 mg/L.
And (4) sampling and diluting the medium tensile strength copper foil with an electrolyte to obtain a sample to be detected.
Adding 20mL of detection matrix solution into a reaction tank 1 shown in figure 1, connecting a three-electrode system, namely a working electrode 2, a reference electrode 3 and an auxiliary electrode 4 (copper plating and copper dissolving reaction occurs on the working electrode 2 during testing, the auxiliary electrode 4 and the working electrode form a polarization loop, the reference electrode 3 has a known constant potential, and provides a potential standard for a research object), connecting an electrochemical workstation, setting parameters, and operating a cyclic voltammetry to obtain an initial voltammetry characteristic curve (basic curve), as shown in figure 2;
adding 1mL of sample to be detected into the reaction tank, and operating the electrochemical workstation to obtain a voltammetry characteristic curve (sample voltammetry characteristic curve) after the sample to be detected is added; adding 0.1mLSPS standard solution into the reaction tank twice, and respectively operating the workstations to obtain 2 voltammetry characteristic curves (a standard voltammetry characteristic curve 1 and a standard voltammetry characteristic curve 2), as shown in FIG. 2;
processing the voltammetry characteristic curve, calculating the corresponding transferred electric quantity according to the integral area of each curve to obtain a sample fitting curve (SPS concentration transferred electric quantity curve), and correcting the determination coefficient R as shown in FIG. 32＝0.99996≥0.999。
Calculating to obtain the SPS concentration C in the electrolyte for the copper foil with medium tensile strength according to the slope of the curveSample (I)：
In the formula TDilution ofThe dilution factor of the electrolyte for the copper foil with the tensile strength is shown as delta Q, the transfer capacity corresponding to the added sample is shown as delta Q, the k slope is the slope of an SPS concentration transfer capacity curve, the V sample is the volume of the sample to be detected, and the V total is the total volume of the solution in the reaction tank.
In summary, according to the technical scheme of the invention, a copper sulfate detection matrix solution is prepared in a quantitative container to prepare an SPS standard solution, an electrolyte sample of the SPS to be detected is added into a reaction tank containing the detection matrix solution, a cyclic voltammetry method is used for analyzing and recording the change of a voltammetry characteristic curve, the SPS standard solution is discontinuously added into the reaction tank after the detection sample is added, the cyclic voltammetry curve before and after the SPS standard solution is added every time is recorded, and the concentration of the SPS in the electrolyte is calculated according to the deviation of the SPS standard solution and the SPS standard solution, so that the interference of other additives in the electrolyte is eliminated, the SPS content in the electrolyte is accurately detected, the regulation and control direction of a production process is accurately guided, and the firm guarantee is provided for the.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A quantitative analysis method for SPS in electrolyte for anti-drawing copper foil is characterized by comprising the following steps:
s1: preparing imitation electrolyte, adding an auxiliary solution into the imitation electrolyte to prepare a detection matrix solution, and adding SPS into the imitation electrolyte to prepare an SPS standard solution;
s2: taking the electrolyte for the medium tensile strength copper foil to be detected, and diluting the electrolyte in a certain proportion to be used as a sample to be detected;
s3: adding a detection matrix solution into a reaction tank of a three-electrode system, activating electrodes by using the three-electrode system, and analyzing and recording a voltammetry characteristic curve of the detection matrix solution as a basic curve after the curve is stable;
s4: adding a sample to be tested into a reaction tank, fully stirring, and recording a voltammetry characteristic curve of the sample by using a cyclic voltammetry method;
s5: adding the SPS standard solution into a reaction tank, fully stirring, recording a standard voltammetry characteristic curve by using a cyclic voltammetry method, and repeating the step;
s6: and analyzing the volt-ampere characteristic curve to obtain a sample fitting curve, and calculating the concentration of the SPS in the sample according to the sample fitting curve.
2. The method for quantitatively analyzing SPS in electrolyte for stretch-proof copper foil according to claim 1, wherein said imitation electrolyte in step S1 comprises H2SO4And CuSO4The auxiliary solution comprises a displacement agent and a brightening agent.
3. The method for quantitatively analyzing SPS in electrolyte for anti-drawing copper foil according to claim 2, wherein in the auxiliary solution, the dislocation agent comprises a main dislocation agent and an auxiliary dislocation agent, the brightener comprises an auxiliary brightener, the concentration of the main dislocation agent is 300-500mg/L, the concentration of the auxiliary dislocation agent is 80-150mg/L, the concentration of the auxiliary brightener is 5-15mg/L, and the SPS concentration in the SPS standard solution is 20-150 mg/L.
4. The method for quantitatively analyzing SPS in electrolyte solution for a stretch-resistant copper foil according to claim 1, wherein the volume of the detection base solution in step S3 is 30 to 50 mL.
5. The method for quantitatively analyzing SPS in electrolyte solution for stretch-resistant copper foil according to claim 1, wherein the volume of the sample to be tested added in step S4 is 1 to 3 mL.
6. The method for quantitatively analyzing SPS in electrolyte solution for stretch-proof copper foil according to claim 1, wherein the number of times of adding the SPS standard solution in step S5 is 2 to 4.
7. The method for quantitatively analyzing SPS in electrolyte for stretch-proof copper foil according to claim 6, wherein the volume of the SPS standard solution added in each case in the step S5 is 0.05-0.25 mL.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114689675A (en) * | 2022-04-29 | 2022-07-01 | 浙江花园新能源股份有限公司 | Electrochemical principle-based quantitative analysis method for additives in electrolytic copper foil plating solution |
| CN115078488A (en) * | 2022-05-24 | 2022-09-20 | 浙江工业大学 | Quantitative analysis method for organic additive in copper electrolytic refining |
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| CN115078488B (en) * | 2022-05-24 | 2024-05-14 | 浙江工业大学 | Quantitative analysis method of organic additive in copper electrorefining |
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Application publication date: 20201225 |