CN115704810B - Method for measuring content of 2-propyne-1-yl 1H-imidazole-1-carboxylate by high performance liquid chromatography - Google Patents
Method for measuring content of 2-propyne-1-yl 1H-imidazole-1-carboxylate by high performance liquid chromatography Download PDFInfo
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- -1 2-propyne-1-yl 1H-imidazole-1-carboxylate Chemical compound 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004128 high performance liquid chromatography Methods 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 89
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000001514 detection method Methods 0.000 claims abstract description 22
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- 239000000945 filler Substances 0.000 claims abstract description 5
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012086 standard solution Substances 0.000 claims description 39
- 238000012417 linear regression Methods 0.000 claims description 18
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- 238000002156 mixing Methods 0.000 claims description 13
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- 239000007924 injection Substances 0.000 claims description 4
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- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
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- SMXSJALRXPANJM-UHFFFAOYSA-N 5-oxooxolane-2-sulfonic acid Chemical compound OS(=O)(=O)C1CCC(=O)O1 SMXSJALRXPANJM-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
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- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a method for measuring the content of 2-propyne-1-yl 1H-imidazole-1-carboxylate in lithium battery electrolyte by a high performance liquid chromatography, which mainly solves the problem that the content of 2-propyne-1-yl 1H-imidazole-1-carboxylate in lithium battery electrolyte cannot be accurately measured. According to the invention, the 2-propyne-1-yl 1H-imidazole-1-carboxylic acid ester in the lithium ion electrolyte can be effectively separated by adopting a high performance liquid chromatograph with a differential detector, a chromatographic column with octadecylsilane chemically bonded silica as a filler and an acetonitrile/water compounded mobile phase, so that the content of the 2-propyne-1-yl 1H-imidazole-1-carboxylic acid ester in the lithium ion electrolyte can be accurately measured; the detection method has the advantages of simplicity, effectiveness, accuracy and convenience.
Description
Technical Field
The invention relates to a method for measuring the content of 2-propyne-1-yl 1H-imidazole-1-carboxylate by high performance liquid chromatography.
Background
Lithium batteries are widely used due to their high operating voltage, high energy density, long cycle life, and the like. The electrolyte is used as the blood of the lithium battery, has great influence on the performance of the lithium battery, and mainly comprises an organic solvent, lithium salt and an additive, the content and the concentration of each component in the electrolyte have important influence on the performance of the electrolyte, and particularly the concentration of each component is an important reference index for judging whether the electrolyte meets the application requirements, so that each component in the electrolyte needs to be accurately quantified.
The 2-propyn-1-yl 1H-imidazole-1-carboxylate has good stability, can be used as an electrolyte additive in electrolyte to improve the performance of a lithium battery, and in order to ensure the electrolyte quality of the lithium battery and the performance of the lithium battery, a determination method capable of accurately carrying out quantitative analysis on the 2-propyn-1-yl 1H-imidazole-1-carboxylate needs to be studied.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a method for measuring the content of 2-propyne-1-yl 1H-imidazole-1-carboxylate in lithium battery electrolyte by using a high performance liquid chromatography method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides an application of a high performance liquid chromatography in detecting the content of 2-propyne-1-yl 1H-imidazole-1-carboxylate in lithium battery electrolyte.
The second aspect of the invention provides a method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in lithium battery electrolyte, wherein the method is high performance liquid chromatography.
Preferably, the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte is detected by using a high performance liquid chromatograph.
Further preferably, the detector used by the high performance liquid chromatograph is a differential detector.
Preferably, the chromatographic column adopted by the high performance liquid chromatograph is a chromatographic column taking octadecylsilane chemically bonded silica as a filler.
Further preferably, the particle diameter (diameter) of the silica gel particles packed in the column is 4.6 μm, and the length of the column is 500mm.
According to some preferred embodiments, the chromatography column is a VP-ODS chromatography column.
Further preferably, the column is formed by connecting two VP-ODS250L×4.6 columns in series.
Preferably, the detection condition of the high performance liquid chromatography is to control the temperature of a column box of the high performance liquid chromatography to be 30-50 ℃, further 35-45 ℃ and further 40 ℃.
Preferably, the temperature of the differential detector is controlled to be 30 to 50 ℃, further 35 to 45 ℃, still further 40 ℃.
Preferably, the column flow rate is controlled to be 0.5 to 1.5mL/min, and further 1.0mL/min.
Preferably, a fixed sample loop is used, and the sample amount is 20 mu L.
Preferably, the lithium battery electrolyte is mixed with the mobile phase for dilution and then detected by the high performance liquid chromatograph. The mass content of the 2-propyne-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte is calculated according to the formulaWherein X% is the mass percentage content of 2-propyne-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte, k is a coefficient, A 1 And n is the dilution multiple of the electrolyte, and 10000 is a constant, wherein n is the peak area of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the diluted lithium battery electrolyte.
Further preferably, the method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte by using the high performance liquid chromatography further comprises the step of detecting a plurality of standard solutions of 2-propyn-1-yl 1H-imidazole-1-carboxylate with different mass concentrations by using the high performance liquid chromatography, and linearly regressing the peak area of the 2-propyn-1-yl 1H-imidazole-1-carboxylate of the standard solution obtained after detection and the mass concentration of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the corresponding standard solution to obtain k.
Preferably, the mobile phase is a mixed solution of acetonitrile and water.
Further preferably, the mobile phase is composed of acetonitrile, water, and (5 to 7): (3-5) by volume ratio.
Still further preferably, the mobile phase is prepared from acetonitrile, water at 3:2 by volume ratio.
According to one specific embodiment of the invention, the method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester in the lithium battery electrolyte by using the high performance liquid chromatography comprises the following steps:
(1) Mixing acetonitrile and water to prepare a mobile phase;
(2) Mixing a standard sample of 2-propyn-1-yl 1H-imidazole-1-carboxylate with the mobile phase to prepare a plurality of standard solutions with different mass concentrations;
(3) Mixing the lithium battery electrolyte with the mobile phase to dilute the electrolyte;
(4) Detecting the standard solution and the diluted electrolyte by adopting a high performance liquid chromatograph;
(5) And (3) carrying out linear regression on the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the standard solution and the mass concentration of the standard solution corresponding to the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the standard solution to obtain a linear regression equation, and calculating the mass content of the 2-propyne-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the lithium battery electrolyte and the linear regression equation.
Preferably, the acetonitrile and the water in the step (1) further comprise the step of filtering the acetonitrile and the water by using a micro-pore filter membrane with a pore diameter of 0.45 μm before mixing.
Preferably, the mass concentration of the plurality of standard solutions in the step (2) is arranged in a gradient manner, and the mass concentration of each standard solution is controlled to be in the range of 10-160 ppm.
Further preferably, the number of the standard solutions is 3 to 8, still further 4 to 6.
Preferably, the dilution factor of the lithium battery electrolyte is controlled to be 95-105 times.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention adopts high performance liquid chromatography to simply and effectively measure the content of the 2-propyne-1-yl 1H-imidazole-1-carboxylate in the lithium ion electrolyte.
Furthermore, the invention can effectively separate 2-propyne-1-yl 1H-imidazole-1-carboxylic acid ester from lithium ion electrolyte by adopting a high performance liquid chromatograph with a differential detector and a chromatographic column with octadecylsilane chemically bonded silica as fillers and an acetonitrile/water compounded mobile phase, and accurately measure the content of the 2-propyne-1-yl 1H-imidazole-1-carboxylic acid ester in the lithium ion electrolyte; the detection method has the advantages of simplicity, effectiveness, accuracy and convenience.
Drawings
FIG. 1 is a liquid chromatogram of a standard sample of example 1 of the present invention diluted to 100 ppm;
FIG. 2 is a liquid chromatogram of sample # 1 in example 1 of the present invention after 100-fold dilution;
FIG. 3 is a liquid chromatogram of electrolyte of sample # 1 in example 1 of the present invention, but without 2-propyn-1-yl-1H-imidazole-1-carboxylate diluted 100-fold;
FIG. 4 is a graph showing the working curves of standard solutions in example 1 of the present invention;
FIG. 5 is a liquid chromatogram of sample # 2 diluted 100-fold in example 1 of the present invention;
FIG. 6 is a chromatogram of the standard sample of comparative example 1 of the present invention diluted to 100 ppm;
FIG. 7 is a chromatogram of sample # 1 in comparative example 1 of the present invention after 100-fold dilution.
FIG. 8 is a GC spectrum of a freshly prepared sample # 1 in comparative example 2 in accordance with the present invention;
FIG. 9 is a GC spectrum of sample # 1 of comparative example 2 of the present invention after 6 hours of placement.
Detailed Description
The commonly used analysis method in lithium battery electrolyte is anion chromatography, which is mainly liquid chromatography using ionic compounds as analysis objects, and anions of 2-propyn-1-yl 1H-imidazole-1-carboxylate after being decomposed in water are hydroxide ions, and based on anion chromatography detection principle, the anion chromatography cannot detect hydroxide ions, so the method is not suitable for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate.
The inventor thinks for the first time that the content of 2-propyne-1-yl 1H-imidazole-1-carboxylate in lithium battery electrolyte is detected by adopting a high performance liquid chromatography method, and the specific detection method is as follows:
(1) Mixing acetonitrile and water to prepare a mobile phase;
(2) Mixing a standard sample of 2-propyn-1-yl 1H-imidazole-1-carboxylate with the mobile phase to prepare a plurality of standard solutions with different mass concentrations;
(3) Mixing the lithium battery electrolyte with the mobile phase to dilute the electrolyte;
(4) Detecting the standard solution and the diluted electrolyte by adopting a high performance liquid chromatograph;
(5) And (3) carrying out linear regression on the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the standard solution and the mass concentration of the standard solution corresponding to the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the standard solution to obtain a linear regression equation, and calculating the mass content of the 2-propyne-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the lithium battery electrolyte and the linear regression equation.
The acetonitrile and the water in the step (1) are mixed in the following proportions (5 to 7): (3-5) by volume ratio.
Further, the acetonitrile, the water were mixed at 3:2 by volume.
Preferably, the acetonitrile and the water further comprise a step of filtering the acetonitrile and the water by using a microporous filtering membrane having a pore size of 0.45 μm before mixing. Through carrying out filtering operation to the mobile phase, can effectively get rid of the impurity in the mobile phase, avoid impurity to block up the condition emergence of chromatographic column.
Further, the acetonitrile, the water to after mixing also include a step of degassing the mobile phase with ultrasound. The mobile phase is easy to generate bubbles when being filtered and mixed, and the separation effect of the chromatographic column can be influenced when the mobile phase with bubbles enters the liquid phase, and the base line is unstable, so that the mobile phase needs to be subjected to ultrasonic degassing before entering the chromatograph.
And (2) arranging the mass concentration of the plurality of standard solutions in a gradient manner, and controlling the mass concentration of each standard solution to be 10-160 ppm.
Further, the number of the standard solutions is 3 to 8, and more preferably 4 to 6.
As a preferred example, the number of standard solutions may be set to 5, and the contents of 2-propyn-1-yl-1H-imidazole-1-carboxylate of 5 standard solutions may be 20ppm, 50ppm, 80ppm, 120ppm, 150ppm, respectively.
The dilution factor of the lithium battery electrolyte in the step (3) is 95-105 times.
The dilution factor of the lithium battery electrolyte is not limited to 95-105 times, the dilution factor is determined by the mass content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte, when the mass content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte is too high, the dilution factor can be increased according to the actual content, and when the mass content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte is too low, the dilution factor can be reduced according to the actual content.
In particular, the differential detector is a waters2414 differential detector, which performs component detection based on different substances having different refractive indices, so that the detector can be used whenever it has a component having a refractive index different from that of the mobile phase. The lithium battery electrolyte is composed of a plurality of components, each component can be accurately quantified only by separating, and the content of the components can be accurately detected by selecting proper mobile phase components and chromatographic columns to enable all the components in a sample to be fully separated.
Further, the chromatographic column in the high performance liquid chromatograph is a chromatographic column using octadecylsilane chemically bonded silica as a filler.
Further, the silica gel particles of the column had a particle diameter of 4.6 μm and the column had a length of 500mm.
The length of the chromatographic column is in direct proportion to the number of the column plates, and different components can be separated by the proper number of the column plates, so that the detection accuracy is improved.
Specifically, the chromatographic column is a VP-ODS chromatographic column.
Further, the column is formed by connecting two VP-ODS250L×4.6 columns in series.
Further, the detection condition of the high performance liquid chromatography is that the temperature of a column box of the high performance liquid chromatography is controlled to be 30-50 ℃, further 35-45 ℃, and further 40 ℃. The temperature of the column box can influence the separation of substances in the chromatographic column, and the temperature of the column box is set at 40 ℃, so that the sensitivity of the liquid chromatographic column can be improved, the resolution of a spectrum peak can be improved, and the detection of the content of 2-propyne-1-yl 1H-imidazole-1-carboxylate is facilitated.
Further, the temperature of the differential detector is controlled to be 30 to 50 ℃, further 35 to 45 ℃, and still further 40 ℃.
Further, the column flow rate was controlled to be 0.5 to 1.5mL/min, and more preferably 1.0mL/min.
Further, a fixed sample loop is used for sample injection, and the sample injection amount is 20uL.
And (2) detecting a plurality of standard solutions of 2-propyn-1-yl 1H-imidazole-1-carboxylic acid esters with different mass concentrations by using the high performance liquid chromatography, and linearly regressing the peak area of the 2-propyn-1-yl 1H-imidazole-1-carboxylic acid esters of the standard solutions obtained after detection and the mass concentration of the 2-propyn-1-yl 1H-imidazole-1-carboxylic acid esters in the corresponding standard solutions.
Further, the mass content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte is detected by using the high performance liquid chromatograph to obtain the peak area of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte, the peak area is brought into the linear regression equation to obtain the mass content of the corresponding 2-propyn-1-yl 1H-imidazole-1-carboxylate, and the mass content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte is obtained through conversion.
Specifically, the mass content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte is calculated according to the formula as followsWherein X% is the mass percentage content of 2-propyne-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte, k is the reciprocal of the slope in the linear regression equation, and A 1 And n is the dilution multiple of the electrolyte, and 10000 is a constant, wherein n is the peak area of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the diluted lithium battery electrolyte.
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The standard sample of the 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester is a commercial product, wherein the purity of the 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester in the standard sample is more than or equal to 99.5%.
Example 1
The high performance liquid chromatography determination method of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte comprises the following steps:
(1) Instrument conditions: the method comprises the steps of adopting a high performance liquid chromatograph waters2414 of a differential detector, wherein a chromatographic column is VP-ODS250L multiplied by 4.6, two chromatographic columns of the same type are used in series, setting the temperature of a column box and the differential detector to be 40 ℃, setting the flow rate of the column to be 1.0mL/min, quantifying the annular sample, and the sample injection amount to be 20uL;
(2) Preparing a mobile phase: the mobile phase is a mixed solution of acetonitrile and water (the volume ratio of acetonitrile to water in the mixed solution=3:2), wherein the acetonitrile is chromatographic purity, the water is chromatographic purity, and the acetonitrile and the water are filtered by a microporous filter membrane of 0.45um and then are used;
(3) Preparing a standard solution: dissolving a standard sample of 2-propyn-1-yl 1H-imidazole-1-carboxylate by using a mobile phase in a stepwise dilution mode, and respectively preparing standard solutions with gradient concentration of 21.5ppm, 49.8ppm, 82.3ppm, 119.7ppm and 152.1ppm for later use;
(4) Sample solution to be measured: the electrolyte sample to be measured is a mixture composed of lithium hexafluorophosphate, a plurality of solvents and additives, wherein the types of additives comprise 2-propyne-1-yl 1H-imidazole-1-carboxylate, and the electrolyte sample is diluted by 95-105 times by using a mobile phase and uniformly mixed for later use;
(5) Instrument preparation: the method comprises the steps of connecting a prepared mobile phase to an instrument, opening a power supply and a computer of a host computer of the instrument, opening 'breeze 2' software, inputting user name starting software, entering a control panel, opening a pump, setting the flow rate of the mobile phase to be 1.0mL/min, selecting a 'shift+1' key on the instrument panel, flushing a reference cell, closing flushing after 30min, entering a baseline checking state, and injecting a sample after the baseline is stable and analyzing the baseline;
(6) The content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the electrolyte after detection is calculated according to the following formula:
wherein X% is the mass percentage of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the electrolyte sample, k is a coefficient, A 1 The peak area of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the solution after the electrolyte sample is treated is shown, n is the dilution multiple of the sample, and 10000 is a constant.
Diluting a standard sample of 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester to 100ppm by taking a mobile phase as a diluting solvent, and then sampling, wherein a chromatogram is shown in figure 1; diluting the electrolyte containing 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester by 100 times by taking the mobile phase as a diluting solvent, and then injecting the sample, wherein a chromatogram is shown in figure 2; the electrolyte containing no 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester is diluted 100 times by taking the mobile phase as a diluting solvent, and then is injected, the chromatogram is shown in figure 3, and the 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester can be detected by adopting high performance liquid chromatography of a differential detector.
After verification, respectively injecting the standard solutions with 5 gradient concentrations into a liquid chromatograph, obtaining a working curve (see figure 4), a linear regression equation and a linear correlation coefficient according to the concentrations of the standard solutions and the response peak areas of the liquid chromatograph, obtaining a linear regression equation y= 4.4536x according to the linear regression equation which is obtained by fitting the linear regression equation with the concentrations and the peak areas in a linear increasing trend shown in figure 4, and determining the coefficient R according to the linear regression equation 2 0.9996, R 2 The linearity of the linear regression equation is good near 1, which indicates that the method for detecting the content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate is feasible, wherein k is 0.2245 obtained by the linear regression equation.
Respectively selecting a mixture of lithium hexafluorophosphate, methyl ethyl carbonate, butylene carbonate, propylene carbonate, ethylene carbonate, ethyl formate, ethyl propionate, 1, 4-sulfobutyrolactone and 2-propyn-1-yl 1H-imidazole-1-carboxylate as a sample No. 1, wherein the mass content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate is 0.10% (sample No. 2), and the electrolyte sample to be detected is lithium hexafluorophosphate, dimethyl carbonate, methyl ethyl carbonate, methyl acetate, ethylene carbonate, propyl acetate, tetrahydrofuran, 1, 3-dioxolane, ethylene carbonate, fluoroethylene carbonate and 2-propyn-1-yl 1H-imidazole-1-carboxylate, wherein the mass content of the 2-propyn-1-yl 1H-imidazole-1-carboxylate is 0.20% (sample No. 5), and respectively carrying out parallel analysis on the mass content of the hexaflumorph-1H-1-yl carboxylic acid in the sample to obtain the parallel table.
TABLE 1
As can be seen from table 1, the relative standard deviation RSD of sample # 1 and sample # 2 are satisfactory and have good reproducibility.
Example 2
Label adding recovery experiment
And adding a certain amount of 2-propyn-1-yl 1H-imidazole-1-carboxylate standard sample into the sample 1 and the sample 2 respectively, and carrying out content analysis on the electrolyte after the addition of the standard sample according to the method for detecting the 2-propyn-1-yl 1H-imidazole-1-carboxylate electrolyte in the embodiment 1, wherein the detection data are shown in Table 2.
TABLE 2
| 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester 0.052% | Recovery value% | Recovery% | |
| Sample # 1 | 0.154 | 0.053 | 101.9 |
| Sample # 2 | 0.251 | 0.050 | 96.2 |
| 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester 0.105% | Recovery value% | Recovery% | |
| Sample # 1 | 0.205 | 0.105 | 100.0 |
| Sample # 2 | 0.307 | 0.107 | 101.9 |
| 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester 0.20% | Recovery value% | Recovery% | |
| Sample # 1 | 0.299 | 0.199 | 99.5 |
| Sample # 2 | 0.403 | 0.203 | 101.5 |
The data analysis of table 2 found that: the detection method of the 2-propyne-1-yl 1H-imidazole-1-carboxylate in the electrolyte product has the standard recovery rate of 95-105% and good analysis accuracy.
Comparative example 1
Anion chromatographic analysis is adopted to carry out anion chromatographic detection on the raw material and electrolyte of the 2-propyn-1-yl 1H-imidazole-1-carboxylate.
Diluting the 2-propyn-1-yl 1H-imidazole-1-carboxylate raw material to 100ppm by using pure water as a solvent, performing anion chromatography detection after ultrasonic treatment for 30min, wherein the anion chromatography is shown in fig. 6, and no effective ion peak appears in the anion chromatography.
Taking sample 1 in example 1 as an example, the electrolyte is diluted by pure water for 100 times and then subjected to ultrasonic treatment for 30min for anion chromatography detection, the anion chromatography is shown in fig. 7, and no effective ion peak appears in the anion chromatography.
Since 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester does not show a peak on anion chromatography, it cannot be analyzed by anion chromatography.
Comparative example 2
In the case of measurement by GC (gas chromatography), taking sample No. 1 in example 1 as an example, GC measurement was performed after the electrolyte sample preparation system was stabilized for 10min, and GC measurement was performed again after the electrolyte was left for 6h, and GC chromatograms are respectively shown in fig. 8 and 9. Wherein the characteristic peak (about 6.6min, oval circled position in fig. 8 and 9) of the 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester in the gas chromatograph is compared with the chromatogram, the detectable area percentage of the 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester is reduced from 0.2983% to 0.0125%, namely the substance on the GC can be along with the prolonged placement time of the electrolyte, and the detectable peak area of the GC method is smaller and smaller. Therefore, 2-propyn-1-yl 1H-imidazole-1-carboxylate cannot be accurately quantified by GC (gas chromatography).
The present invention has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present invention and to implement the same, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. A method for detecting the content of 2-propyne-1-yl 1H-imidazole-1-carboxylate in lithium battery electrolyte is characterized by comprising the following steps: the detection method is characterized in that the detection method is a high performance liquid chromatography, lithium battery electrolyte is firstly mixed with a mobile phase for dilution and then is detected by a high performance liquid chromatograph, wherein a detector adopted by the high performance liquid chromatograph is a differential detector, a chromatographic column adopted by the high performance liquid chromatograph is a chromatographic column taking octadecylsilane bonded silica gel as a filler, and the mobile phase is a mixed solution of acetonitrile and water with the volume ratio of 3:2.
2. The method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to claim 1, wherein the method comprises the following steps: the diameter of the silica gel particles filled in the chromatographic column is 4.6 μm, and the length of the chromatographic column is
500mm; the chromatographic column is formed by connecting two VP-ODS250L multiplied by 4.6 chromatographic columns in series; the differential detector is a waters2414 differential detector.
3. The method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to claim 1, wherein the method comprises the following steps: the detection conditions of the high performance liquid chromatography are as follows: the temperature of the column box of the high performance liquid chromatograph is controlled to be 30-50 ℃ and the temperature of the differential detector is controlled to be 30-50 ℃.
4. The method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to claim 1, wherein the method comprises the following steps: when the high performance liquid chromatography is adopted for detection, the flow rate of the column is controlled to be 0.5-1.5 mL/min.
5. The method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to claim 1, wherein the method comprises the following steps: when the high performance liquid chromatography is adopted for detection, the sample injection amount is controlled to be 20 mu L.
6. The method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to claim 1, wherein the method comprises the following steps: the mass content of the 2-propyne-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte is calculated according to the formulaWherein X% is the mass percentage of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte, k is a coefficient, and A1 is 2-propyn-1-yl 1H-imidazole-1 in the diluted lithium battery electrolyte-peak area of carboxylate, n is dilution multiple of the electrolyte and 10000 is constant.
7. The method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to claim 6, wherein the method comprises the following steps: the method for detecting the content of the 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester in the lithium battery electrolyte by using the high performance liquid chromatography further comprises the steps of detecting a plurality of standard solutions of the 2-propyn-1-yl 1H-imidazole-1-carboxylic acid ester with different mass concentrations by using the high performance liquid chromatography, and obtaining the 2-propyn-1-yl 1H-imidazole-1-17-one of the standard solutions after detection
And (3) linearly regressing the peak area of the carboxylate and the mass concentration of the 2-propyn-1-yl 1H-imidazole-1-carboxylate in the corresponding standard solution to obtain k.
8. The method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) Mixing acetonitrile and water to prepare a mobile phase;
(2) Mixing a standard sample of 2-propyn-1-yl 1H-imidazole-1-carboxylate with the mobile phase to prepare a plurality of standard solutions with different mass concentrations;
(3) Mixing the lithium battery electrolyte with the mobile phase to dilute the electrolyte;
(4) Detecting the standard solution and the diluted electrolyte by adopting a high performance liquid chromatograph;
(5) And (3) carrying out linear regression on the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the standard solution and the mass concentration of the standard solution corresponding to the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the standard solution to obtain a linear regression equation, and calculating the mass content of the 2-propyne-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to the peak area of the 2-propyne-1-yl 1H-imidazole-1-carboxylate of the lithium battery electrolyte and the linear regression equation.
9. The method for detecting the content of 2-propyn-1-yl 1H-imidazole-1-carboxylate in the lithium battery electrolyte according to claim 8, wherein the method comprises the following steps: the acetonitrile and the water in the step (1) also comprise the step of filtering the acetonitrile and the water by using a micro-pore filter membrane with the pore diameter of 0.45 mu m before mixing;
the mass concentration of the standard solutions in the step (2) is arranged in a gradient manner, and the mass concentration range of each standard solution is controlled to be 10-160 ppm;
and (3) controlling the dilution factor of the lithium battery electrolyte to be 95-105 times.
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