CN1614406A - Quantitatively analyzing method for fluohydric acid in lithium ion battery electrolyte - Google Patents
Quantitatively analyzing method for fluohydric acid in lithium ion battery electrolyte Download PDFInfo
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Abstract
A quantitative analysis method includes diluting lithium ion cell electrolyte in absolute ethyl alcohol or methyl alcohol, using MOH as titrant, applying automatic potentiometric titration, using (CoXV20)/(1000XM) to confirm titrimetric curve as Co referring to tritrant concentration, V referring to consumed tritrant volume ml, 20 referring to HF molecular weight and M referring to electrolyte weight, using potentiometric titrator to carry out second order derivation of titrimetric curve for cnofirming titrimetric end point.
Description
Technical Field
The invention relates to the technical field of production and manufacture of lithium ion battery electrolyte, in particular to a quantitative analysis method for hydrofluoric acid in lithium ion battery electrolyte.
Background
A trace amount of hydrofluoric acid in a nonaqueous electrolyte for a lithium ion battery has a great influence on the capacity, cycle life, and safety of the battery. Thus, in lithiumThe hydrofluoric acid content must be strictly monitored during the production, storage, transportation of the ion battery electrolyte, and during the manufacturing of the battery. However, the reported techniques in this respect are very rare. At present, tetrabutylammonium hydroxide (NBu) is generally used4OH) as a titrant and bromothymol blue (BTB) as an indicator, and hydrogen fluoride in a nonaqueous system was measured from the effect of the reaction between hydrogen fluoride and tetrabutylammonium hydroxide in an electrolyte solution in an anhydrous methanol solvent (measurement of hydrogen fluoride in a nonaqueous system) ) But a side reaction accompanied by the reaction (A) ) This causes some errors in the analysis results, and the tetrabutylammonium hydroxide is very expensive (for example, measurement method by MERCK). To solve the problem, the invention patent application No. 01130017.5 of china also discloses a method using sodium methoxide as a titrant, which has certain improvement in reducing the detection cost, but the common point of the method and the above methods is that BTB is used as an indicator, and the endpoint is judged by a visual inspection method, which may generate certain systematic errors. In addition, in order to improve the stability of the electrolyte, some stabilizers are generally added in industry to improve the stability of lithium hexafluorophosphate, inhibit the generation of hydrogen fluoride and adsorb hydrogen fluoride, and most of the stabilizers are lewis bases, so that the electrolyte generally presents weak alkalinity (the pH value is about 7-9), and the pH value of the BTB color change point is about 7, therefore, the sudden pH value jump point of the solution during dripping is probably not consistent with the color change point of BTB, and great error is brought to the test result.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a quantitative analysis method for hydrofluoric acid in lithium ion battery electrolyte. The method can overcome the problem that the pH value jump point of the solution is inconsistent with the color-changing point of the indicator in the existing titration method, thereby greatly improving the accuracy of the measurement result.
The invention is provided withThe technical scheme is as follows: quantification of hydrofluoric acid in the lithium ion battery electrolyteDiluting the lithium ion battery electrolyte into solvent anhydrous methanol or anhydrous ethanol which does not need drying treatment according to the proportion of adding 2.5-3.0 g into 50ml of solvent, taking MOH as a titrant, determining a titration curve by adopting an automatic potentiometric titration method, and performing second-order derivation on the titration curve by using a potentiometric titrator so as to determine a titration end point; using the formula (C)0X V20)/(1000 x m) calculating the end point value, where C0Is the concentration mol/L of the titrant, V is the volume ml of the titrant consumed, 20 is the molecular weight of HF, and m is the weight g of the electrolyte.
In order to better implement the invention, M in the titrant MOH comprises alkali metals such as lithium, sodium, potassium and the like, particularly KOH; the concentration of the titrant is 0.0100 mol/L-0.1000 mol/L; the solvent is absolute ethyl alcohol or absolute methanol (the water content is 0.15-0.2%) which does not need drying treatment, and the absolute ethyl alcohol which does not need drying treatment is particularly preferred; the lithium ion battery electrolyte comprises an organic solvent and a lithium salt, wherein the organic solvent comprises one or more mixed solvents of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), gamma-butyrolactone (gamma-BL), Dimethoxyethane (DME) and Tetrahydrofuran (THF), and the lithium salt comprises LiCF3SO3、LiPF6、LiBF4、LiClO4、LiAsF6、LiN(CF3SO2)2One or more than one mixture.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides an accurate analysis method suitable for hydrofluoric acid in lithium ion battery electrolyte on the basis of respectively researching the influence of titrant and solvent on quantitative analysis of hydrofluoric acid and respectively analyzing and comparing test results of an indicator method and an automatic potentiometric titration method. Compared with the prior art, the method has the advantages that the measurement accuracy is greatly improved (the measurement result in the prior art is low, the deviation degree is larger after the organic amine stabilizer is added into the electrolyte, the difference of the test results in the electrolyte with larger acidity and higher stabilizer content is very obvious, and the deviation reaches 18.2%).
The contrast experiment proves that the test result of taking tetrabutylammonium hydroxide as a titrant is larger than that of othertitrants; the titration curve measured by using sodium methoxide as a titrant is the most gentle, the jump is not obvious, and the deviation of the measured parallel results is large (mainly caused by the weak alkalinity of sodium methoxide and the slow reaction with acid); the titration leaps of NaOH and KOH as titrants are obvious, and the accuracy of the parallel measurement result is better than that of the two titrants, but the measurement result is slightly higher than that of KOH due to the higher reactivity of NaOH and a solvent. KOH has strong alkalinity, fast reaction with acid, obvious curve jump, and no reaction with anhydrous methanol and anhydrous ethanol. Tests show that the titration curves in absolute methanol are all smoother than those in absolute ethanol; the absolute ethyl alcohol is not further dried, and the existence of trace moisture not only does not influence the measurement result, but also makes the titration jump more obvious and is more beneficial to the judgment of the end point. Therefore, KOH is preferably used as a titrant, absolute ethyl alcohol which is not subjected to further drying treatment is used as a solvent, the titration end point is most easily judged, the test result is most accurate, the used titrant and the solvent are cheap, the titration process is not required to be carried out in a glove box, and the method is a test method which is very suitable for industrial analysis.
Drawings
FIG. 1 is a titration curve of four titrants in two solvents, namely absolute methanol and absolute ethanol, in example four of the present invention;
FIG. 2 is an acidity titration curve of ethanol solvent of different water content according to example four of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Some of the reagents and instruments used in the examples include:
methanol (chromatographically pure, manufactured by Merk, germany); absolute ethanol (analytically pure); 3A molecular sieve; benzoic acid (standard), dried under vacuum at 80 ℃ for 8 hours; bromothymol blue (BTB), dried under vacuum at 100 ℃ for 8 hours; 0.1mol/L NaOH solution (analytically pure, produced by Merk, Germany); 0.1mol/L potassium hydroxide ethanol solution (analytical purity, produced by Merk, Germany); tetrabutylammonium hydroxide; 0.1mol/L isopropanol solution (analytical grade, Merk, Germany); sodium methoxide (analytical purity).
EC. DMC, EMC: the content is more than or equal to 99.95 percent, and the water content is less than 10 ppm. LiPF6: the content is more than or equal to 99.95 percent, and the content of HF is less than 100 ppm. Organic base (represented by N): the content is more than or equal to 99.9 percent, and the water content is less than 100 ppm. Deionized water.
Metrohm model 798 potentiometric titrator (manufactured by Metrohm company, switzerland); a long-life composite pH electrode; a moisture meter model Metrohm 831 KF (manufactured by Metrohm company, switzerland); electronic balance (accuracy 0.0001g, sartorius); a glove box: argon atmosphere, no water and no oxygen; the preparation and sampling of the electrolyte are carried out in the glove box; 10ml PE syringe.
Example one
Firstly, selecting a dried 10ml PE injector, taking 8ml of lithium ion battery electrolyte in a glove box, sealing a needle by using silica gel, and transferring the injector to the air; the electrolyte of the lithium ion battery is prepared from diethyl carbonate (DEC), gamma-butyrolactone (gamma-BL) and LiCF3SO3、LiBF4Mixing the components, wherein gamma-BL: DEC is 1: 2(w), and the concentration of two lithium salts is 0.5 mol/L;
secondly, adding 50.0ml of anhydrous methanol (without drying treatment and with the water content of 0.15%) into a titration cup by using a pipette, adding 2 g of electrolyte (the amount of the electrolyte is weighed by balance and injected to be accurate to 0.1mg), and starting stirring;
thirdly, selecting potassium hydroxide with the concentration of 0.0100mol/L as a titrant, starting titration, inputting the dosage of the electrolyte into a potentiometric titrator, inputting a second-order derivation program (provided by Metrohm company of Switzerland) andacidity calculation formula (C)0X V20)/(1000 x m), wherein C0Is the concentration mol/L of the titrant, V is the volume ml of the consumed titrant, 20 is the molecular weight of HF, and m is the weight g of the electrolyte; adjusting titration step length according to the content of hydrogen fluoride in the electrolyte, wherein the titration step length is 1/10-1/20 of the volume of a consumed titrant at the titration end point, carrying out uniform titration, stopping titration after the end point appears and a titration curve is very smooth, and taking the final jump end point;
fourthly, according to the test result, whether the titration step length is 1/10-1/20 of the volume of the consumed titrant at the titration end point or not is judged, and if not, the titration step length is adjusted to repeat the third step; results were measured in 3 replicates and averaged.
Example two
Firstly, selecting a dried 10ml PE injector, taking 8ml of lithium ion battery electrolyte in a glove box, sealing a needle by using silicagel, and transferring the injector to the air; the electrolyte of the lithium ion battery is prepared from Propylene Carbonate (PC), Dimethoxyethane (DME) and LiClO4、LiAsF6Mixed composition, wherein PC and DME are 1 to 2(w), and the concentration of two lithium salts is 0.5 mol/L;
secondly, adding 50.0ml of absolute ethyl alcohol (without drying treatment and with the water content of 0.2%) into a titration cup by using a pipette, adding 2.5g of electrolyte (the amount of the electrolyte is weighed by using balance and is accurately injected to 0.1mg), and starting stirring;
thirdly, sodium hydroxide with the concentration of 0.0500mol/L is selected as a titrant, titration is started, the dosage of the electrolyte is input into a potentiometric titrator, and a second-order derivation program (provided by Metrohm company of Switzerland) and an acidity calculation formula (C) are input0X V20)/(1000 x m), wherein C0Is the concentration mol/L of the titrant, V is the volume ml of the consumed titrant, 20 is the molecular weight of HF, and m is the weight g of the electrolyte; adjusting titration step length according to the content of hydrogen fluoride in the electrolyte, wherein the titration step length is 1/10-1/20 of the volume of a consumed titrant at the titration end point, carrying out uniform titration, stopping titration after the end point appears and a titration curve is very smooth, and taking the final jump end point;
fourthly, according to the test result, whether the titration step length is 1/10-1/20 of the volume of the consumed titrant at the titration end point or not is judged, and if not, the titration step length is adjusted to repeat the third step; results were measured in 3 replicates and averaged.
EXAMPLE III
Firstly, selecting a dried 10ml PE injector, taking 8ml of lithium ion battery electrolyte in a glove box, sealing a needle by using silica gel, and transferring the injector to the air; the electrolyte of the lithium ion battery consists of PC, methyl carbonate (DMC), Tetrahydrofuran (THF) and LiN (CF)3SO2)2Mixing to form a mixture, wherein PC, DMC, THF is 2: 3: 1(w), and the concentration of lithium salt is 1 mol/L;
secondly, adding 50.0ml of absolute ethyl alcohol (without drying treatment and with the water content of 0.2%) into a titration cup by using a pipette, adding 3 g of electrolyte (the amount of the electrolyte is weighed by using balance and injected to be accurate to 0.1mg), and starting stirring;
thirdly, selecting lithium hydroxide with the concentration of 0.1000mol/L as a titrant, starting titration, inputting the dosage of the electrolyte into a potentiometric titrator, and inputting a second-order derivation program (provided by the Switzerland Metrohm company) and an acidity calculation formula (C)0X V20)/(1000 x m), wherein C0Is the concentration mol/L of the titrant, V is the volume ml of the consumed titrant, 20 is the molecular weight of HF, and m is the weight g of the electrolyte; adjusting titration step length according to the content of hydrogen fluoride in the electrolyte, wherein the titration step length is 1/10-1/20 of the volume of a consumed titrant at the titration end point, carrying out uniform titration, stopping titration after the end point appears and a titration curve is very smooth, and taking the final jump end point;
fourthly, according to the test result, whether the titration step length is 1/10-1/20 of the volume of the consumed titrant at the titration end point or not is judged, and if not, the titration step length is adjusted to repeat the third step; results were measured in 3 replicates and averaged.
Example four
To further illustrate the invention, this example was carried out in a manner comparable to the prior art indicator method:
comparative indicator method: taking 8ml of electrolyte from a dried 10ml PE syringe in a glove box, sealing a needle by using silica gel, adding 50ml of absolute ethyl alcohol and 4-5 drops of BTB into a titration cup by using a pipette, adding 3-4 g (accurate to 0.1mg) of electrolyte, uniformly mixing while shaking until the solution turns blue, recording the using amount of a titrant, and carrying out parallel determination for 3 times.
The following lithium ion battery electrolytes were formulated in glove boxes, but not limited to the following formulations:
A、EC∶DMC∶EMC＝1∶1∶1(w)，LiPF6: 1mol/L (this expression is optional)
B、EC∶DMC∶EMC＝1∶1∶1(w)，LiPF6: 1mol/L, adding a stabilizerN0.1％(w)
C. Adding a little water to A to make its water content about 100ppm, sealing and standing at 45 deg.C for 24 hr, adding stabilizer N0.5% (w)
D、EC∶PC∶DMC∶EMC＝2∶1∶2∶3(w)，LiPF6: 1mol/L, adding a stabilizer N1% (w).
Using 0.1mol/L ethanol solution of sodium hydroxide and ethanol solution of potassium hydroxide with dried ethanol (H) in a glove box2O<20ppm) was diluted 10-fold, and a 0.1mol/L tetrabutylammonium hydroxide isopropanol solution was diluted 10-fold with methanol to prepare a 0.01mol/L methanol solution of sodium methoxide. The four solutions were calibrated with reference benzoic acid.
Comparison of test methods: electrolyte B, C was measured in parallel three times each using KOH as the titrant and absolute ethanol as the solvent, one using potentiometric titration and the other using indicator.
Titrant to solvent comparison: electrolyte a was assayed in dry absolute ethanol and methanol with four titrants: about 6ml of sample was taken in a 10ml syringe in a glove box, the syringe was sealed with silica gel, and the measurement was carried out in a room with about 2.5g per injection and carried out in triplicate by potentiometric titration. The effect of titrant and solvent on the assay results was compared.
KOH was used as a titrant, electrolytes A and D were measured in absolute ethyl alcohol (water content-2000 ppm) and further dried absolute ethyl alcohol (water content-10 ppm), respectively, and the influence of the presence of trace moisture on the test results was compared.
Measurement results of hydrofluoric acid:
(1) concentration calibration of titrants
TABLE 1 concentration of four titrants (unit: mol/L)
| Titrant | 1 | 2 | 3 | Average result |
| NBu4OH | 0.0098 | 0.0010 | 0.0098 | 0.0099 |
| NaOCH3 | 0.0097 | 0.0099 | 0.0098 | 0.0098 |
| NaOH | 0.0101 | 0.0102 | 0.0101 | 0.0101 |
| KOH | 0.0102 | 0.0103 | 0.0102 | 0.0102 |
(2) Comparison of test methods
In industrial applications, in order to increase the stability of the electrolyte, lewis bases (for example, organic amines) are generally added as stabilizers in an amount such that the electrolyte is near neutral or more basic (pH)07-9) in the prior art, and the problem is not considered in the prior art, so that the pH value of the final point of the determination is probably not determined by adopting the prior artWithin the color change range of the indicator, a large error occurs if the stabilizer is strongly basic or is present in a high amountHigh, pH of the electrolyte0The larger the deviation of the result may be.
Table 2 shows the results of the tests of electrolytes A and B of the invention (autopotential titration method) and of the prior art (indicator method), and Table 3 shows the results of the tests of electrolyte C of the two methods, in which the pH is comparedzIs the pH at the end of the test, the titrant is KOH and the solvent is undried ethanol, and the measurements are carried out 3 times in parallel.
TABLE 2 Effect of stabilizers on hydrofluoric acid quantitation
| Electrolyte sample | pH0 | m1(ppm) | pHz1 | m2(ppm) | pHz2 | (M2-M1)/ M2×100％ |
| A | 5.4 | 13.9 | 6.3 | 15.0 | 6.7 | 8.5 |
| 14.5 | 6.5 | 15.6 | 6.9 | |||
| 14.3 | 6.4 | 16.1 | 6.7 | |||
| B | 6.8 | 14.0 | 7.2 | 16.3 | 7.5 | 8.8 |
| 14.2 | 7.1 | 15.9 | 7.6 | |||
| 15.0 | 7.2 | 15.3 | 7.5 |
Note: m is1As a result of the indicator method test, M1Is the average value of m2Is the result of potentiometric titration, M2Is the average thereof.
Table 3 results of two methods for testing electrolyte C electrolyte
pH0m1(ppm) pHz1m2(ppm) pHz2(M2-M1)/M2×100％
259.7 7.6 305.6 7.9
7.2 230.4 7.5 298.9 7.8 18.2
249.7 7.6 300.3 7.9
Note: m is1As a result of the indicator method test, M1Is the average value of m2Is the result of potentiometric titration, M2Is the average thereof.
As can be seen from the data in Table 2, the addition of the stabilizer had little effect on the total acidity of the electrolyte, but only increased the pH of the electrolyte. Analysis of the data in conjunction with Table 3 shows that the results of the indicator method are much smaller than those of the potentiometric titration method, and that this deviation is smaller (8.5%) in electrolytes with a low acidity content (<30 ppm); the results of the two methods after the stabilizer is added into the electrolyte are greatly different, particularly the results of the tests in the electrolyte with larger acidity (more than or equal to 50ppm) and higher stabilizer content (more than or equal to 0.5) are very obvious (18.2%), and the results of the tests in the indicator method are very poor in accuracy, which indicates that the indicator method is not suitable for the acidity test in the current electrolyte system.
(3) Comparative analysis of titrant and solvent
Table 4 shows the results of 3 replicates of electrolyte a tested in methanol and ethanol, respectively, using four titrants tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide and sodium methoxide, by autopotential titration. As shown in FIG. 1, the titration jump in ethanol B is more pronounced than in methanol A (a, tetrabutylammonium hydroxide, B, sodium hydroxide, c, potassium hydroxide, d, sodium methoxide). The data in table 4 show that the accuracy of KOH among the four titrants is best. Tetrabutylammonium hydroxide was tested as a titrant with greater results than the other three titrants. The jump of sodium methoxide is flat, which makes it difficult to select the jump end point. The accuracy of the test results using KOH as the titrant was best, with a standard deviation of less than 1% for both methanol and ethanol solvents.
TABLE 4 test results (unit: ppm) of different titrants in methanol and ethanol, respectively
| Titrant | Tetrakis (butyl) hydroxide Radical ammonium | Sodium hydroxide | Potassium hydroxide | Sodium methoxide | |
| Methanol | Measured value | 28.3，27.7，27.0 | 16.8，21.8，12.4 | 14.4，16.3，15.8 | 15.2，11.0，16.9 |
| Standard deviation Difference S (%) | 0.65 | 4.70 | 0.98 | 3.04 | |
| Ethanol | Measured value | 22.8，18.6，16.9 | 16.5，16.9，17.3 | 11.7，11.3，12.0 | 16.6，18.0，15.1 |
| Standard deviation Difference S (%) | 3.04 | 0.40 | 0.35 | 1.45 | |
(4) Influence of micro-moisture on test results
In the prior art, ethanol is dried by a molecular sieve, in the embodiment, the 3A molecular sieve is used for drying ethanol, ethanol before and after drying is respectively used as a solvent for testing, the tested electrolytes are a (diagram a) and a (diagram B), and table 5 shows test results, which shows that the test results of ethanol before and after drying are not very different, and the test results of ethanol without drying are better in accuracy. As shown in FIG. 2, curve a is for ethanol (H)2O: 2171.6 ppm); curve b is for ethanol (H)2O: 23.6 ppm). It can be seen that the jump in the titration curve is steeper in the undried ethanol than in the dried ethanol, and the data in table 5 show that the results measured in the undried ethanol are also somewhat more accurate. From the results, it can be analyzed that the influence of trace moisture (0.15-0.2%) in the pure ethanol on the test results can be ignored, and the experimental results show that the moisture is favorable for theexistenceAnd judging the end point.
TABLE 5 influence of solvent Water content on quantitative analysis of hydrofluoric acid
| Water content (ppm) | Electrolyte solution | Acidity (ppm) | RSD(％) |
| 2171.6 | A | 15.0，13.0，13.6 | 1.03 |
| D | 115.3，117.1，114.4 | 1.37 | |
| 23.6 | A | 15.2，13.2，14.5 | 1.01 |
| D | 114.0，118.3，116.7 | 2.17 |
As described above, the present invention can be preferably realized.
Claims (7)
1. A quantitative analysis method for hydrofluoric acid in lithium ion battery electrolyte is characterized in that the lithium ion battery electrolyte is diluted to a solvent without drying treatment according to the proportion that 2.5-3.0 g of the lithium ion battery electrolyte is added into 50ml of the solventIn water methanol or absolute ethanol, MOH is used as a titrant, an automatic potentiometric titration method is adopted to determine a titration curve, and a potentiometric titrator is used for carrying out second-order derivation on the titration curve, so that a titration end point is determined; using the formula (C)0X V20)/(1000 x m) calculating the end point value, where C0Is the concentration mol/L of the titrant, V is the volume ml of the titrant consumed, 20 is the molecular weight of HF, and m is the weight g of the electrolyte.
2. The method of claim 1, wherein M in the titrant MOH comprises lithium, sodium and potassium as alkali metals.
3. The method of claim 1 or 2, wherein the titrant is KOH.
4. The method of claim 1, wherein the titrant concentration is 0.0100mol/L to 0.1000 mol/L.
5. The method of claim 1, wherein the solvent is anhydrous ethanol or anhydrous methanol without drying treatment, and the water content is 0.15-0.2%.
6. The method for quantitatively analyzing the hydrofluoric acid in the lithium ion battery electrolyte according to claim 1 or 5, wherein the solvent is absolute ethyl alcohol without drying treatment, and the water content is 0.15-0.2%.
7. The method of claim 1, wherein the electrolyte comprises an organic solvent and a lithium salt, and the organic solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ -butyrolactone, dimethyl carbonate, or a mixture thereofOne or more mixed solvents of oxyethane and tetrahydrofuran, wherein the lithium salt comprises LiCF3SO3、LiPF6、LiBF4、LiClO4、LiAsF6、LiN(CF3SO2)2One or more than one mixture.
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