CN111257470A - Pretreatment method for detecting organic solvent in electrolyte and detection method - Google Patents
Pretreatment method for detecting organic solvent in electrolyte and detection method Download PDFInfo
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Abstract
The invention relates to a pretreatment method and a detection method for detecting an organic solvent of an electrolyte. The pretreatment method comprises the following steps: taking an organic solvent different from the organic solvent contained in the electrolyte; activating an ion exchange type solid phase extraction column by using the organic solvent; loading the electrolyte, passing through a column, and collecting filtrate; and eluting by adopting the organic solvent, collecting filtrate, and combining the filtrates collected twice to obtain the electrolyte to be tested. The pretreatment method can fully remove lithium salt in the organic solvent of the electrolyte, is beneficial to detecting the organic solvent, is simple and convenient to operate, and more importantly, can prevent corrosive substances in the electrolyte from entering detection equipment, corroding instruments, reducing column loss, prolonging the service life of a chromatographic column, reducing test cost, improving test accuracy and being used for detecting production and research and development products.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a pretreatment method and a detection method for detecting an organic solvent of an electrolyte.
Background
The lithium ion battery is a green high-energy environment-friendly battery appearing in 90 s of the 20 th century, and is widely applied to the fields of portable electronic products, electric tools, electric bicycles and the like at present. The organic electrolyte is an important component of the lithium ion battery, and plays a role in charge transmission between a positive electrode and a negative electrode in the battery, so that the usability and the safety of the battery are directly influenced by the impurity type and the content accuracy of the electrolyte.
The organic electrolyte is an important component of the lithium ion battery, plays a role in charge transmission between a positive electrode and a negative electrode in the battery, and has important influence on the main performances of the battery, such as working temperature, specific energy, cycle efficiency, safety and the like, and the content of the components also has important influence on the performance of the battery, so that each battery manufacturer requires accurate quantification of the components of the electrolyte, and the organic electrolyte generally comprises two parts, namely electrolyte lithium salt and an organic solvent. Most of the organic solvent tests are currently evaluated by gas chromatography.
Related reports show that substances with high corrosivity, such as phosphorus oxyfluoride, phosphorus fluoride, hydrofluoric acid and the like, which are generated in the storage process or the high-temperature process of the electrolyte, have a large destructive effect on the stability of the packing of the gas chromatographic column, so that more columns are lost in the testing process, the stability and the accuracy of a testing result are reduced, and the service life of the chromatographic column is seriously shortened; with the increase of the testing frequency, the corrosion of hydrofluoric acid corrosive gas to the gas chromatograph is increased, the precision of the instrument is influenced, and the failure rate of the equipment is increased. Therefore, it is important to establish a rapid, simple, accurate, safe and effective detection method for the organic components of the electrolyte. On one hand, the lithium salt organic components can be accurately monitored and analyzed, on the other hand, the service life of equipment and consumables can be improved, and the detection cost is reduced.
Disclosure of Invention
Based on the above, the pretreatment method for detecting the organic solvent in the electrolyte provided by the invention can fully separate the lithium salt in the organic solvent in the electrolyte, is beneficial to detecting the organic solvent, is simple and convenient to operate, more importantly, can prevent corrosive substances in the electrolyte from entering detection equipment, corroding instruments, reducing column loss, prolonging the service life of a chromatographic column, reducing the test cost, and meanwhile, avoids the interference of unknown miscellaneous peaks and column loss peaks on quantification and stability, so that the test result is more accurate, the repeatability is better, and the pretreatment method can be used for detecting products in production and research and development.
The specific technical scheme of the pretreatment method for detecting the organic solvent in the electrolyte is as follows:
a pretreatment method for electrolyte test comprises the following steps:
taking an organic solvent different from the organic solvent contained in the electrolyte;
activating an ion exchange type solid phase extraction column by using the organic solvent;
loading the electrolyte, passing through a column, and collecting filtrate;
and eluting by adopting the organic solvent, collecting filtrate, and combining the filtrates collected twice to obtain the electrolyte to be tested.
In one preferred embodiment, the organic solvent is selected from a carbonate-based solvent, acetone or acetonitrile.
In one preferred embodiment, the carbonate-based solvent is selected from ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, or ethylene carbonate.
In one preferred embodiment, the ion exchange type solid phase extraction column is selected from a SAX solid phase extraction column, a WAX weak anion exchange solid phase extraction column, and a MAX mixed type anion exchange solid phase extraction column.
In one preferred embodiment, the amount of the electrolyte used in the loading is 0.5 mL-2 mL.
The invention also provides a detection method of the organic solvent in the electrolyte.
The specific technical scheme is as follows:
a detection method of an organic solvent in electrolyte comprises the step of processing the electrolyte by adopting the pretreatment method.
In one preferred embodiment, the method further comprises the following steps:
preparing a standard solution with a specific concentration;
and carrying out gas chromatography test on the standard solution and the electrolyte to be tested.
In one preferred embodiment, the chromatographic conditions of the gas chromatographic assay comprise: the column was DB-1701.
In one preferred embodiment, the chromatographic conditions of the gas chromatographic assay comprise: the initial temperature of the column temperature is 50 ℃, the temperature is kept for 5min, then the temperature is increased to 80 ℃ at the speed of 10 ℃/min, the temperature is kept for 2min, then the temperature is increased to 240 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 min.
In one preferred embodiment, the chromatographic conditions of the gas chromatographic assay comprise: the column flow rate is 1ml/min to 3ml/min, more preferably, the column flow rate is 2.0 ml/min.
In one preferred embodiment, the chromatographic conditions of the gas chromatographic assay comprise: the amount of sample is 0.2. mu.L-2. mu.L, more preferably, the amount of sample is 0.5. mu.L.
In one preferred embodiment, the chromatographic conditions of the gas chromatographic assay comprise: the split ratio is (28-32): 1, more preferably, the split ratio is 30: 1.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a solid phase extraction technology to pretreat the electrolyte, and specifically comprises the following steps: activating an ion exchange type solid phase extraction column by adopting an organic solvent different from the electrolyte, then passing the electrolyte through the column, collecting filtrate, then continuously eluting by using the organic solvent different from the electrolyte, collecting filtrate, and combining the filtrates collected twice to serve as the electrolyte to be detected. Through the operation, can fully get rid of the lithium salt in the electrolyte organic solvent, be favorable to detecting organic solvent, easy and simple to handle, more importantly, can stop corrosive substance in the electrolyte and enter into check out test set, corrosion instrument reduces the post and runs off, improves the life-span of chromatographic column, reduce the test cost, and simultaneously, the interference of unknown miscellaneous peak and post loss peak to ration and stability has been avoided, make the test result more accurate, the repeatability is better, can be used to the detection of production and research and development product.
The pretreatment method for the electrolyte can be used for detecting the content of the organic solvent in the electrolyte by gas chromatography. By carrying out the pretreatment on the electrolyte, the gas chromatogram with a flatter baseline, less impurity peaks and less column loss can be obtained, the influence of interference peaks can be reduced, the stability of a detection result is ensured, the repeatability is high, the accuracy is improved, and meanwhile, the damage of an instrument is reduced and the service life of a chromatographic column is prolonged.
Drawings
FIG. 1 shows IC test spectra for different pre-treatments;
FIG. 2 is a GC test spectrum of different pretreatment modes;
FIG. 3 is a partial enlarged view of GC test spectra for different pretreatment modes.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The lithium ion battery is a green high-energy environment-friendly battery appearing in 90 s of the 20 th century, and is widely applied to the fields of portable electronic products, electric tools, electric bicycles and the like at present. The organic electrolyte is an important component of the lithium ion battery, and plays a role in charge transmission between a positive electrode and a negative electrode in the battery, so that the usability and the safety of the battery are directly influenced by the impurity type and the content accuracy of the electrolyte.
The organic electrolyte generally consists of two parts, namely electrolyte lithium salt and organic solvent, and the content of the components has important influence on the performance of the battery, so that the components of the electrolyte need to be accurately quantified. In particular, the organic solvent in the electrolyte is quasi-quantitatively determined.
Most of the organic solvent tests are currently evaluated by gas chromatography.
However, relevant reports show that substances with high corrosivity, such as phosphorus oxyfluoride, phosphorus fluoride, hydrofluoric acid and the like, which are generated in the storage process or the high-temperature process of the electrolyte, have a large destructive effect on the stability of the packing of the gas chromatographic column, so that more columns are lost in the testing process, the stability and the accuracy of the testing result are reduced, and the service life of the chromatographic column is seriously shortened; with the increase of the testing frequency, the corrosion of hydrofluoric acid corrosive gas to the gas chromatograph is increased, the precision of the instrument is influenced, and the failure rate of the equipment is increased. Therefore, it is important to establish a rapid, simple, accurate, safe and effective detection method for the organic components of the electrolyte. On one hand, the lithium salt organic components can be accurately monitored and analyzed, on the other hand, the service life of equipment and consumables can be improved, and the detection cost is reduced.
In order to solve the problems, the invention provides a pretreatment method for detecting an organic solvent in an electrolyte.
The specific technical scheme is as follows:
a pretreatment method for detecting an organic solvent in an electrolyte comprises the following steps:
taking an organic solvent different from the organic solvent contained in the electrolyte;
activating an ion exchange type solid phase extraction column by using the organic solvent;
loading the electrolyte, passing through a column, and collecting filtrate;
and eluting by adopting the organic solvent, collecting filtrate, and combining the filtrates collected twice to obtain the electrolyte to be tested.
In the pretreatment method of the invention, an organic solvent which is not contained in the electrolyte to be tested is determined first, and the subsequent operation is carried out. The interference to the quantification of the organic solvent in the electrolyte is avoided.
The organic solvent can be an organic solvent commonly used in the field of electrolyte.
The organic solvent includes, but is not limited to, carbonate solvents, acetone, or acetonitrile.
The carbonate-based solvent includes, but is not limited to, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, or ethylene carbonate.
The extraction column selected by the invention is an ion exchange type solid phase extraction column, and is more beneficial to removing lithium salt in the organic solvent of the electrolyte compared with other types of extraction columns, and the subsequently obtained gas chromatography spectrogram (GC spectrogram) has stable baseline and few miscellaneous peaks.
The ion exchange type solid phase extraction column includes but is not limited to SAX solid phase extraction column, WAX weak anion exchange solid phase extraction column, MAX mixed type anion exchange solid phase extraction column.
In some preferred embodiments, the ion-exchange type solid phase extraction column is a dieka proellut SAX.
It is understood that the electrolyte is preferably used in an amount of 0.5mL to 2mL when the sample is loaded.
And after the electrolyte passes through the column, collecting filtrate, eluting the solid phase extraction column by using the selected organic solvent, and washing the residual electrolyte organic solvent in the solid phase extraction column to obtain the filtrate. And then combining the filtrates collected twice to obtain the electrolyte to be detected, and finishing the pretreatment operation.
It can be understood that, after the filtrates collected twice are combined, the method further comprises the step of filtering to fix the volume to obtain the electrolyte to be measured.
Adopt above-mentioned solid-phase extraction technique to carry out the preliminary treatment to electrolyte, can fully get rid of the lithium salt in the electrolyte organic solvent, be favorable to detecting organic solvent, and easy and simple to handle, more importantly, can stop corrosive substance in the electrolyte to enter into check out test set, corrode the instrument, reduce the post loss, improve the life-span of chromatographic column, reduce the test cost, and simultaneously, the interference of unknown miscellaneous peak and post loss peak to ration and stability has been avoided, make the test result more accurate, the repeatability is better, can be used to the detection of production and research and development product.
The invention also provides a detection method of the electrolyte organic solvent.
The specific technical scheme is as follows:
the detection method of the organic solvent of the electrolyte comprises the step of processing the electrolyte by adopting the pretreatment method.
It is understood that the organic solvent in the electrolyte can be quantitatively detected using gas chromatography. Before the electrolyte is subjected to sample introduction and analysis, the electrolyte is treated by adopting the pretreatment method.
Preferably, the method for detecting an organic solvent in an electrolyte further comprises:
preparing a standard solution with a specific concentration;
and carrying out gas chromatography test on the standard solution and the electrolyte to be tested.
It should be understood that the preparation of the standard solution with a specific concentration means that the standard solution with a specific concentration is prepared according to the kind of the organic solution in the electrolyte to be tested, and the preparation of the standard solution may adopt a preparation method that is common in the art, and the invention is not limited herein.
According to the method, a single-standard method is adopted to detect the sample, and the content of the organic solvent in the electrolyte to be detected is obtained according to the peak area of the standard solution with the known concentration and the peak area of the electrolyte to be detected.
In some preferred embodiments, the gas chromatograph is a gas chromatograph (FID detector).
In some preferred embodiments, the chromatographic conditions of the gas chromatograph comprise: the column was DB-1701.
It will be appreciated that the column may also be other columns of the same type.
In some preferred embodiments, the chromatographic conditions of the gas chromatograph comprise: the initial temperature of the column temperature is 50 ℃, the temperature is kept for 5min, then the temperature is increased to 80 ℃ at the speed of 10 ℃/min, the temperature is kept for 2min, then the temperature is increased to 240 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 min.
In some preferred embodiments, the chromatographic conditions of the gas chromatograph comprise: the column flow rate is 1ml/min to 3ml/min, more preferably, the column flow rate is 2.0 ml/min.
In some preferred embodiments, the chromatographic conditions of the gas chromatograph comprise: the amount of sample is 0.2. mu.L-2. mu.L, more preferably, the amount of sample is 0.5. mu.L.
In some preferred embodiments, the chromatographic conditions of the gas chromatograph comprise: the split ratio is (28-32): 1, more preferably, the split ratio is 30: 1.
The detection method for the organic solvent in the electrolyte has the advantages of high precision and accuracy, stable detection result and high repeatability.
The following description will be given with reference to specific examples.
Example 1
Instruments and experimental drugs: a pipette, an ion exchange type solid phase extraction column (DIKMA ProElut SAX), a beaker, a volumetric flask, a PET bottle, a methyl ethyl carbonate solvent with the content of more than or equal to 99.99 percent, and an electrolyte (containing organic solvents such as dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, ethyl propionate, vinylene carbonate, fluorobenzene, fluoroethylene carbonate, adiponitrile, succinonitrile, 1, 3-propane sultone and 1,3, 6-hexane tricarbonitrile).
(1) Sample pretreatment
Activating the small column: activating the SAX solid phase extraction column by ethyl methyl carbonate, collecting filtrate at the lower end of the small column by using a small beaker, and treating the filtrate to be scrapped.
Column passing: accurately remove 1mL of electrolyte onto the column using a pipettor and collect the filtrate.
And (3) elution: and then adding ethyl methyl carbonate along the wall of the column tube for washing for 4-5 times, combining the filtrate collected by the column and the filtrate collected by washing, and fixing the volume after filtering to obtain the electrolyte to be detected.
(2) Ion Chromatography (IC) testing
And (3) carrying out an Ion Chromatography (IC) test on the electrolyte to be tested, and representing the effect of removing lithium salt and substances with higher corrosivity.
The chromatographic conditions of the ion chromatography are as follows:
a chromatographic column: supp 5; eluent: 10.0mmoL sodium carbonate solution (30% acetonitrile); flow rate: 0.5 mL/min; column temperature: at 40 ℃. Regeneration liquid: 0.5 per mill sulfuric acid aqueous solution; ultrapure water.
The ion chromatographic spectrum is shown in figure 1.
(3) Gas Chromatography (GC) testing
And (3) performing Gas Chromatography (GC) test on the electrolyte to be tested by adopting a single-standard method, and quantitatively detecting the organic solvent of the electrolyte.
The chromatographic conditions of the gas chromatograph are as follows:
gas chromatographs (FID detectors); a chromatographic column: DB-1701; the initial temperature of the column temperature is 50 ℃, the temperature is kept for 5min, then the temperature is increased to 80 ℃ at the speed of 10 ℃/min, the temperature is kept for 2min, then the temperature is increased to 240 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 min; the column flow rate is 2.0ml/min, the sample injection amount is 0.5 mu L, and the split ratio is 30: 1.
The gas chromatography spectrum of the electrolyte to be detected is shown in fig. 2, and the local amplification spectrum is shown in fig. 3.
(4) Precision experiment
Referring to the method of (3), the organic solvents of two known electrolyte formulations were quantitatively analyzed by GC to obtain the precision of the method, which was compared with the theoretical value, and the results of the precision experiments are shown in tables 1 and 2:
TABLE 1 precision test results I
| Components | Theoretical value | 1 | 2 | 3 | 4 | Average | RSD(％) |
| Fluorobenzene (%) | 3.9 | 3.94 | 3.93 | 4.00 | 3.98 | 3.96 | 0.73 |
| Propionic acid ethyl ester (%) | 15.7 | 15.72 | 15.66 | 15.84 | 15.83 | 15.78 | 0.48 |
| Carbonic acid ethyl ester (%) | 19.6 | 19.63 | 19.60 | 19.72 | 19.72 | 19.67 | 0.32 |
| Vinylene carbonate (%) | 0.3 | 0.30 | 0.30 | 0.30 | 0.30 | 0.30 | 0.71 |
| Fluoroethylene carbonate (%) | 5 | 4.99 | 5.00 | 4.97 | 4.99 | 4.99 | 0.07 |
| Ethylene carbonate (%) | 19.6 | 19.40 | 19.47 | 19.19 | 19.19 | 19.30 | 0.77 |
| Propylene carbonate (%) | 19.6 | 19.60 | 19.66 | 19.61 | 19.62 | 19.61 | 0.07 |
| Adiponitrile (%) | 2 | 2.00 | 2.00 | 1.99 | 2.00 | 2.00 | 0.04 |
TABLE 2 precision test results II
| Components | Theoretical value | 1 | 2 | 3 | 4 | Average | RSD(％) |
| Carbonic acid ethyl ester (%) | 8 | 8.02 | 7.99 | 8.02 | 8.01 | 8.01 | 0.16 |
| Propyl propionate (%) | 35.5 | 35.36 | 35.11 | 35.19 | 35.18 | 35.21 | 0.45 |
| Fluoroethylene carbonate (%) | 6.0 | 6.05 | 6.08 | 6.09 | 6.07 | 6.07 | 0.59 |
| Ethylene carbonate (%) | 20.0 | 19.93 | 20.06 | 19.97 | 19.99 | 19.99 | 0.24 |
| Propylene carbonate (%) | 10.0 | 10.08 | 10.12 | 10.12 | 10.11 | 10.11 | 0.50 |
| Succinonitrile (%) | 1.5 | 1.50 | 1.52 | 1.51 | 1.52 | 1.51 | 0.66 |
| 1, 3-propane sultone (%) | 4.0 | 4.05 | 4.09 | 4.05 | 4.05 | 4.06 | 0.79 |
| 1,3, 6-Hexane Tricarbonitrile (%) | 1.0 | 1.00 | 1.01 | 1.03 | 1.02 | 1.02 | 1.27 |
As can be seen from tables 1 and 2, the gas chromatography detection method has high precision and accuracy, stable detection result and high repeatability.
Comparative example 1
The comparative example provides a detection method of an organic solvent in an electrolyte, which is basically the same as the detection method of example 1, and is different from the pretreatment method only in that the comparative example adopts a saturated sodium carbonate solution to pretreat the electrolyte, and the specific detection steps are as follows:
instruments and experimental drugs: pipettor, volumetric flask, saturated aqueous sodium carbonate solution, acetone, electrolyte (containing organic solvent such as dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, ethyl propionate, vinylene carbonate, fluorobenzene, fluoroethylene carbonate, adiponitrile, succinonitrile, 1, 3-propane sultone, and 1,3, 6-hexane trinitrile).
(1) Sample pretreatment
Accurately transferring 1mL of electrolyte into a volumetric flask by using a pipettor, adding a small amount of acetone for dilution, shaking up, accurately weighing 1mL of saturated sodium carbonate aqueous solution, then fixing the volume to 10mL by using acetone, shaking up, standing, and taking supernatant, namely the electrolyte to be measured.
(2) Ion Chromatography (IC) testing
And (3) carrying out an Ion Chromatography (IC) test on the electrolyte to be tested, and representing the effect of removing lithium salt and substances with higher corrosivity.
The chromatographic conditions of the ion chromatography are as follows:
a chromatographic column: supp 5; eluent: 10.0mmoL sodium carbonate solution (30% acetonitrile); flow rate: 0.5 mL/min; column temperature: at 40 ℃. Regeneration liquid: 0.5 per mill sulfuric acid aqueous solution; ultrapure water.
The ion chromatographic spectrum is shown in figure 1.
(3) Gas Chromatography (GC) testing
And carrying out Gas Chromatography (GC) test on the electrolyte to be tested.
The chromatographic conditions of the gas chromatograph are as follows:
gas chromatographs (FID detectors); a chromatographic column: DB-1701; the initial temperature of the column temperature is 50 ℃, the temperature is kept for 5min, then the temperature is increased to 80 ℃ at the speed of 10 ℃/min, the temperature is kept for 2min, then the temperature is increased to 240 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 min; the column flow rate is 2.0ml/min, the sample injection amount is 0.5 mu L, and the split ratio is 30: 1.
The gas chromatography spectrum of the electrolyte to be detected is shown in fig. 2, and the local amplification spectrum is shown in fig. 3.
Comparative example 2
The comparative example provides a detection method of an organic solvent in an electrolyte, which is basically the same as the detection method of example 1, and is different from the pretreatment method only in that the comparative example uses an IC pretreatment column-H column for pretreatment, and the specific detection steps are as follows:
instruments and experimental drugs: syringe, pipettor, volumetric flask, deionized water, acetone, electrolyte (containing organic solvents such as dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, ethyl propionate, vinylene carbonate, fluorobenzene, fluoroethylene carbonate, adiponitrile, succinonitrile, 1, 3-propane sultone, and 1,3, 6-hexane trinitrile).
(1) Sample pretreatment
Activating the small column: the H column was activated with deionized water, then excess water was removed by syringe purging and the H column was rinsed 3 times with ethyl methyl carbonate.
Column passing: accurately remove 1mL of electrolyte onto the column using a pipettor and collect the filtrate.
And (3) elution: and then adding ethyl methyl carbonate along the wall of the column tube for washing for 4-5 times, combining the filtrate collected by the column and the filtrate collected by washing, and fixing the volume after filtering to obtain the electrolyte to be detected.
(2) Ion Chromatography (IC) testing
And (3) carrying out an Ion Chromatography (IC) test on the electrolyte to be tested, and representing the effect of removing lithium salt and substances with higher corrosivity.
The chromatographic conditions of the ion chromatography are as follows:
a chromatographic column: supp 5; eluent: 10.0mmoL sodium carbonate solution (30% acetonitrile); flow rate: 0.5 mL/min; column temperature: at 40 ℃. Regeneration liquid: 0.5 per mill sulfuric acid aqueous solution; ultrapure water.
The ion chromatographic spectrum is shown in figure 1.
(3) Gas Chromatography (GC) testing
And carrying out Gas Chromatography (GC) test on the electrolyte to be tested.
The chromatographic conditions of the gas chromatograph are as follows:
gas chromatographs (FID detectors); a chromatographic column: DB-1701; the initial temperature of the column temperature is 50 ℃, the temperature is kept for 5min, then the temperature is increased to 80 ℃ at the speed of 10 ℃/min, the temperature is kept for 2min, then the temperature is increased to 240 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 min; the column flow rate is 2.0ml/min, the sample injection amount is 0.5 mu L, and the split ratio is 30: 1.
The gas chromatography spectrum of the electrolyte to be detected is shown in fig. 2, and the local amplification spectrum is shown in fig. 3.
Comparative example 3
The comparative example provides a detection method of an organic solvent in an electrolyte, which is basically the same as the detection method of example 1, and is different from the detection method in that the electrolyte is not pretreated, and the specific detection steps are as follows:
(1) ion Chromatography (IC) testing
And (3) carrying out an Ion Chromatography (IC) test on the electrolyte to be tested, and representing the effect of removing lithium salt and substances with higher corrosivity.
The chromatographic conditions of the ion chromatography are as follows:
a chromatographic column: supp 5; eluent: 10.0mmoL sodium carbonate solution (30% acetonitrile); flow rate: 0.5 mL/min; column temperature: at 40 ℃. Regeneration liquid: 0.5 per mill sulfuric acid aqueous solution; ultrapure water.
The ion chromatographic spectrum is shown in figure 1.
(2) Gas Chromatography (GC) testing
And carrying out Gas Chromatography (GC) test on the electrolyte to be tested.
The chromatographic conditions of the gas chromatograph are as follows:
gas chromatographs (FID detectors); a chromatographic column: DB-1701; the initial temperature of the column temperature is 50 ℃, the temperature is kept for 5min, then the temperature is increased to 80 ℃ at the speed of 10 ℃/min, the temperature is kept for 2min, then the temperature is increased to 240 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 min; the column flow rate is 2.0ml/min, the sample injection amount is 0.5 mu L, and the split ratio is 30: 1.
The gas chromatography spectrum of the electrolyte to be detected is shown in fig. 2, and the local amplification spectrum is shown in fig. 3.
As can be seen from fig. 1-3, the electrolyte is pretreated by the pretreatment method described in example 1, and compared with the pretreatment methods of comparative examples 1-3, the ion chromatogram shows that the lithium salt of the electrolyte sample pretreated by the SAX column is obviously not peaked at the positions of 25min and 50min, which indicates that the lithium salt in the organic solution of the electrolyte is sufficiently removed and separated. After the electrolyte organic solvent after the lithium salt is fully removed and separated is detected by gas chromatography, a gas chromatography spectrogram with a flatter baseline, fewer impurity peaks and less column loss is presented, the interference of unknown impurity peaks and column loss peaks on quantification and stability is solved, the test result is more accurate, and the repeatability is better; in addition, the problems of column loss reduction, increase of the service life of the chromatographic column and reduction of the test cost are solved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A pretreatment method for detecting an organic solvent in an electrolyte is characterized by comprising the following steps:
taking an organic solvent different from the organic solvent contained in the electrolyte;
activating an ion exchange type solid phase extraction column by using the organic solvent;
loading the electrolyte, passing through a column, and collecting filtrate;
and eluting by adopting the organic solvent, collecting filtrate, and combining the filtrates collected twice to obtain the electrolyte to be tested.
2. The pretreatment method for detecting an organic solvent in an electrolyte according to claim 1, wherein the organic solvent is selected from a carbonate solvent, acetone, and acetonitrile.
3. The pretreatment method for detecting an organic solvent in an electrolyte according to claim 2, wherein the carbonate-based solvent is selected from ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, and ethylene carbonate.
4. The pretreatment method for detecting the organic solvent in the electrolyte according to claim 1, wherein the ion exchange type solid phase extraction column is selected from SAX solid phase extraction column, WAX weak anion exchange solid phase extraction column, and MAX mixed type anion exchange solid phase extraction column.
5. The pretreatment method for detecting an organic solvent in an electrolyte according to any one of claims 1 to 4, wherein the amount of the electrolyte used in the sample application is 0.5 mL-2 mL.
6. A method for detecting an organic solvent in an electrolytic solution, comprising the step of treating the electrolytic solution by the pretreatment method according to any one of claims 1 to 4.
7. The method for detecting the organic solvent in the electrolyte according to claim 6, further comprising:
preparing a standard solution with a specific concentration;
and carrying out gas chromatography test on the standard solution and the electrolyte to be tested.
8. The method for detecting the organic solvent in the electrolyte according to claim 7, wherein the chromatographic conditions of the gas chromatography detection comprise: the column was DB-1701.
9. The method for detecting the organic solvent in the electrolyte according to claim 7, wherein the chromatographic conditions of the gas chromatography detection comprise: the initial temperature of the column temperature is 50 ℃, the temperature is kept for 5min, then the temperature is increased to 80 ℃ at the speed of 10 ℃/min, the temperature is kept for 2min, then the temperature is increased to 240 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 min.
10. The method for detecting the organic solvent in the electrolyte according to any one of claims 7 to 9, wherein the chromatographic conditions of the gas chromatography detection comprise: the column flow rate is 2.0ml/min, the sample injection amount is 0.5 mu L, and the split ratio is 30: 1.
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