CN110702847A - Method for quickly measuring sulfate radical content of vanadium battery electrolyte through temperature titration - Google Patents
Method for quickly measuring sulfate radical content of vanadium battery electrolyte through temperature titration Download PDFInfo
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- CN110702847A CN110702847A CN201911018438.1A CN201911018438A CN110702847A CN 110702847 A CN110702847 A CN 110702847A CN 201911018438 A CN201911018438 A CN 201911018438A CN 110702847 A CN110702847 A CN 110702847A
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- barium chloride
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/02—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using precipitation
Abstract
The invention discloses a method for quickly measuring the sulfate radical content of vanadium battery electrolyte by temperature titration, which belongs to the technical field of sulfate radical content measurement and comprises the following steps: (1) quantitatively weighing vanadium battery electrolyte, placing the vanadium battery electrolyte in a titration cup, diluting, connecting a temperature titration system, starting a stirrer, starting a temperature titrator to titrate with a barium chloride standard solution at a fixed speed, and recording the volume of the barium chloride standard solution consumed when the titration end point is reached; (2) performing a blank test by using distilled water according to the step (1), and recording the volume of the barium chloride standard solution consumed; (3) and (3) calculating the content of sulfate radicals in the electrolyte according to the amount of the barium chloride consumed in the step (1) and the step (2). According to the invention, the content of sulfate in the vanadium battery electrolyte is rapidly determined by adopting a temperature titration method, a detection result can be obtained within about half an hour, and the requirement of rapid determination and real-time monitoring of the vanadium battery electrolyte is met.
Description
Technical Field
The invention belongs to the technical field of sulfate radical content determination, and particularly relates to a method for quickly determining the sulfate radical content of vanadium battery electrolyte through temperature titration.
Background
The vanadium battery electrolyte uses a mixed solution of vanadium sulfate and sulfuric acid with different valence states, and the composition of acid radicals influences the stability, viscosity and conductivity of the solution, so that the efficiency of the battery is influenced. Therefore, the rapid quantitative analysis of the sulfate ion concentration in the electrolyte is very important for the production of the electrolyte of the all-vanadium redox flow battery, the real-time monitoring and operation control of an energy storage system, and the design and maintenance of the system.
At present, sulfate radical detection methods mainly comprise gravimetric methods, titration methods, spectrophotometry, ion chromatography and the like. The sulfate content in the vanadium battery electrolyte is high, and the determination is usually performed by adopting a classic barium sulfate gravimetric method, but the method can be completed within one to two days, and the operation requirements of rapid detection and real-time monitoring are difficult to meet. Potentiometric titration for measuring sulfate is also an indirect detection method, and the content of sulfate can be calculated according to the concentration of vanadium in various valence states. Spectrophotometry and ion chromatography are mostly used for measuring the content of low-content sulfate radicals.
Disclosure of Invention
The invention aims to provide a method for quickly measuring the sulfate radical content of electrolyte of a vanadium cell by temperature titration, which comprises the following steps:
(1) quantitatively weighing vanadium battery electrolyte, placing the vanadium battery electrolyte in a titration cup, diluting, connecting a temperature titration system, starting a stirrer, starting a temperature titrator to titrate with a barium chloride standard solution at a fixed speed, and recording the volume of the barium chloride standard solution consumed when the titration end point is reached;
(2) performing a blank test by using distilled water according to the step (1), and recording the volume of the barium chloride standard solution consumed;
(3) and (3) calculating the content of sulfate radicals in the electrolyte according to the amount of the barium chloride consumed in the step (1) and the step (2).
The method for quickly measuring the sulfate radical content of the vanadium battery electrolyte through temperature titration comprises the following steps:
weighing anhydrous sodium sulfate to prepare sodium sulfate solutions with different concentrations, titrating the sodium sulfate solutions respectively with the prepared barium chloride solutions, recording titration end point volumes respectively, and making a linear regression curve according to the consumption volume of the barium chloride solution and the addition amount of the anhydrous sodium sulfate, wherein the concentration of the barium chloride solution is the reciprocal of the slope of the curve.
According to the method for quickly measuring the sulfate radical content of the vanadium battery electrolyte through temperature titration, the concentration of the barium chloride standard solution is 0.5 mol/L.
According to the method for quickly measuring the sulfate radical content of the vanadium battery electrolyte through temperature titration, the amount of the vanadium battery electrolyte weighed is 0.1-0.5 mL.
In the method for quickly measuring the sulfate radical content of the vanadium battery electrolyte by temperature titration, in the step (1), 50mL of water is added for dilution.
According to the method for quickly measuring the sulfate radical content of the vanadium battery electrolyte through temperature titration, the dropping speed of the barium chloride standard solution is 1-1.5 ml/min.
According to the method for quickly measuring the sulfate radical content of the vanadium battery electrolyte through temperature titration, the sensing temperature measuring range of the temperature titrator is 0-60 ℃, and the precision is 0.00001 ℃.
According to the method for quickly measuring the sulfate radical content of the vanadium battery electrolyte by temperature titration, the calculation formula of the sulfate radical content is as follows:
sulfate radical content in SO4 2-The calculation formula is as follows:
C SO4 2-(mol/L)＝(V2-V1)×C÷V
wherein: c SO4 2-(mol/L) means the molar concentration of sulfate radicals in the electrolyte, mol/L;
v2: the electrolyte consumes the volume of the standard barium chloride solution, namely ml;
v1: blank consumption of barium chloride standard solution volume, ml;
v: the volume of the obtained electrolyte solution is ml during measurement;
c: concentration of barium chloride standard solution, mol/L.
The invention has the beneficial effects that:
compared with the prior art, the method for rapidly determining the sulfate content in the vanadium battery electrolyte by using the temperature titration method has the advantages that the test and the application are obtained in the production inspection, the method is high in accuracy, good in reproducibility, convenient to operate and high in automation degree, the detection result can be obtained within about half an hour, and the requirement of rapid determination and real-time monitoring of the vanadium battery electrolyte is met.
Drawings
FIG. 1 is a titration curve of barium chloride according to the present invention, wherein 1 is a plot of the volume of the titrant versus the temperature of the reaction system, and 2 is a titration second reciprocal curve;
FIG. 2 is a calibration curve of the barium chloride titrant of the present invention.
Detailed Description
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
An instrument and reagent
The temperature titrator is matched with a precision burette, a temperature titration electrode, a special adiabatic titration cup, a stirring table and the like. The sensing temperature measuring range of the temperature titrator is 0-60 ℃, and the precision is 0.00001 ℃.
Barium chloride solution: 0.5 mol/L.
The anhydrous sodium sulfate was guaranteed to be superior pure, the test water was ultrapure water, and the resistivity was 18.0 M.OMEGA.. multidot.cm.
Two test methods
2.1 calibration of barium chloride titrant
Weighing 3.5555g of anhydrous sodium sulfate, fixing the volume to 50mL, respectively taking 1mL, 2mL, 3mL, 4mL and 5mL of sodium sulfate solution, placing the sodium sulfate solution in a sealed titration cup, adding ultrapure water into the titration cup until the total volume is 50mL, connecting a temperature titration system, starting a stirrer, and titrating to an end point by using a temperature titrator at a liquid adding speed of 1mL/min and 0.5mol/L of barium chloride solution under rapid stirring. Linear regression was performed based on the barium chloride solution consumption volume (y, mL) and the anhydrous sodium sulfate addition (x, mmol).
The calibration of the barium chloride standard solution adopts 0.07111g, 0.1422g, 0.2133g, 0.2844g and 0.3555g of anhydrous sodium sulfate 5 points to make a curve.
The titration curve is shown in FIG. 1 and the calibration curve is shown in FIG. 2.
From fig. 2, it can be calculated that the titration volume is linear with the sodium sulfate consumed, y is 2.134x +0.085, and the correlation coefficient R is2＝0.9999，C(BaCl2)＝1/2.134＝0.4686mol/L。
2.2 sample testing and results calculation
Accurately transferring 0.1-0.5 mL of electrolyte sample into a closed titration cup, adding 50mL of ultrapure water, connecting a temperature titration system, starting a stirrer, and titrating with the calibrated barium chloride solution to the end point. The volume of barium chloride solution consumed V2 was recorded. A blank test was run with distilled water following the procedure described above and the volume V1 of barium chloride standard solution consumed was recorded. And calculating the sulfate radical content in the electrolyte.
Sulfate radical content in SO4 2-The calculation formula is as follows:
C SO4 2-(mol/L)＝(V2-V1)×C÷V
wherein: c SO4 2-(mol/L) means the molar concentration of sulfate radicals in the electrolyte, mol/L;
v2: the electrolyte consumes the volume of the standard barium chloride solution, namely ml;
v1: blank consumption of barium chloride standard solution volume, ml;
v: the volume of the obtained electrolyte solution is ml during measurement;
c: concentration of barium chloride standard solution, mol/L.
EXAMPLE 1 sample analysis
Respectively taking 0.1 mL, 0.2mL, 0.3 mL, 0.4 mL and 0.5mL of electrolyte samples of the vanadium redox battery, placing the electrolyte samples in a titration cup, adding 50mL of high-purity water, connecting a temperature titration system, starting a stirrer, titrating with a calibrated barium chloride solution at a liquid adding speed of 1mL/min by using a temperature titrator under the condition of rapid stirring, recording the volume of the consumed barium chloride solution, and calculating the sulfate radical content in the electrolyte. A blank test was performed using distilled water according to the above procedure. The titration data obtained are shown in Table 1.
TABLE 1 results of sulfate test at different sampling volumes
The results show that the experimental results of 5 different sampling amounts are consistent.
Example 2 gravimetric comparison with barium sulfate
Respectively taking 0.5mL of a sample No. 1 and a sample No. 2 of the vanadium redox battery electrolyte, placing the samples in a titration cup, adding 50mL of high-purity water, connecting a temperature titration system, starting a stirrer, titrating with a calibrated barium chloride solution at a liquid adding speed of 1.3mL/min by using a temperature titrator under the condition of rapid stirring, recording the volume of the consumed barium chloride solution, and calculating the sulfate radical content in the electrolyte. A blank test was performed using distilled water according to the above procedure. The measurement was repeated 6 times, and the Relative Standard Deviation (RSD) of the measured value and the relative deviation from the measurement result of the sulfate gravimetric method were calculated, and the results are shown in Table 2.
TABLE 2 comparison of the results of this method with sulfate gravimetric method
As can be seen from Table 2: the RSD of the measured value obtained by the method is between 0.42 and 0.99 percent, the results of the temperature titration method and the barium sulfate gravimetric method are identical, and the relative deviation is between 0.38 and 1.10 percent.
Example 3 spiking recovery test
Respectively taking 0.2mL of No. 1 vanadium battery electrolyte sample, placing the sample into 3 titration cups, and then respectively adding 0.3386mmol, 0.6771mmol and 1.0157mmol of SO4 2-Adding 50mL of high-purity water (added in the form of a sodium sulfate solution), connecting a temperature titration system, starting a stirrer, titrating with a calibrated barium chloride solution at a liquid adding speed of 1mL/min by using a temperature titrator under the condition of rapid stirring, recording the volume of the consumed barium chloride solution, and calculating the sulfate radical content in the electrolyte. A blank test was performed using distilled water according to the above procedure. The measured values and recovery rates were calculated and the results are shown in Table 3.
TABLE 3 recovery test results
Example 4 spiking recovery test
Respectively taking 0.2mL of No. 2 vanadium redox battery electrolyte sample, placing the sample into 3 titration cups, and then respectively adding0.6771mmol, 1.3542mmol and 2.0313mmol of SO are added4 2-Adding 50mL of high-purity water (added in the form of a sodium sulfate solution), connecting a temperature titration system, starting a stirrer, titrating with a calibrated barium chloride solution at a liquid adding speed of 1.5mL/min by using a temperature titrator under the condition of rapid stirring, recording the volume of the consumed barium chloride solution, and calculating the sulfate radical content in the electrolyte. A blank test was performed using distilled water according to the above procedure. The measured values and recovery rates were calculated and the results are shown in Table 4.
TABLE 4 recovery test results
Claims (8)
1. The method for quickly measuring the sulfate radical content of the vanadium battery electrolyte through temperature titration is characterized by comprising the following steps of:
(1) quantitatively weighing vanadium battery electrolyte, placing the vanadium battery electrolyte in a titration cup, diluting, connecting a temperature titration system, starting a stirrer, starting a temperature titrator to titrate with a barium chloride standard solution at a fixed speed, and recording the volume of the barium chloride standard solution consumed when the titration end point is reached;
(2) performing a blank test by using distilled water according to the step (1), and recording the volume of the barium chloride standard solution consumed;
(3) and (3) calculating the content of sulfate radicals in the electrolyte according to the amount of the barium chloride consumed in the step (1) and the step (2).
2. The method for quickly measuring the sulfate radical content of the vanadium redox battery electrolyte according to claim 1 by temperature titration, wherein the calibration method of the barium chloride standard solution is as follows:
weighing anhydrous sodium sulfate to prepare sodium sulfate solutions with different concentrations, titrating the sodium sulfate solutions respectively with the prepared barium chloride solutions, recording titration end point volumes respectively, and making a linear regression curve according to the consumption volume of the barium chloride solution and the addition amount of the anhydrous sodium sulfate, wherein the concentration of the barium chloride solution is the reciprocal of the slope of the curve.
3. The method for quickly measuring the sulfate radical content of the vanadium redox battery electrolyte according to claim 1 by temperature titration is characterized in that: the concentration of the barium chloride standard solution is 0.5 mol/L.
4. The method for quickly measuring the sulfate radical content of the vanadium redox battery electrolyte according to claim 1 by temperature titration is characterized in that: the amount of the electrolyte of the vanadium redox battery is 0.1-0.5 mL.
5. The method for quickly measuring the sulfate radical content of the vanadium redox battery electrolyte according to claim 1 by temperature titration is characterized in that: in step (1), the dilution means the addition of 50mL of water.
6. The method for quickly measuring the sulfate radical content of the vanadium redox battery electrolyte according to claim 1 by temperature titration is characterized in that: the dropping speed of the barium chloride standard solution is 1-1.5 ml/min.
7. The method for quickly measuring the sulfate radical content of the vanadium redox battery electrolyte according to claim 1 by temperature titration is characterized in that: the sensing temperature measuring range of the temperature titrator is 0-60 ℃, and the precision is 0.00001 ℃.
8. The method for quickly measuring the sulfate radical content of the vanadium redox battery electrolyte according to claim 1 by temperature titration is characterized in that the calculation formula of the sulfate radical content is as follows:
sulfate radical content in SO4 2-The calculation formula is as follows:
C SO4 2-(mol/L)＝(V2-V1)×C÷V
wherein: c SO4 2-(mol/L) means the molar concentration of sulfate radicals in the electrolyte, mol/L;
v2: the electrolyte consumes the volume of the standard barium chloride solution, namely ml;
v1: blank consumption of barium chloride standard solution volume, ml;
v: the volume of the obtained electrolyte solution is ml during measurement;
c: concentration of barium chloride standard solution, mol/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114264769A (en) * | 2021-12-23 | 2022-04-01 | 江阴江化微电子材料股份有限公司 | Component concentration detection method of electronic-grade mixed acid system |
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| CN114264769A (en) * | 2021-12-23 | 2022-04-01 | 江阴江化微电子材料股份有限公司 | Component concentration detection method of electronic-grade mixed acid system |
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