CN115184477B - Method for detecting ether compound DOL and DME in lithium-sulfur battery electrolyte - Google Patents
Method for detecting ether compound DOL and DME in lithium-sulfur battery electrolyte Download PDFInfo
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- CN115184477B CN115184477B CN202210450343.2A CN202210450343A CN115184477B CN 115184477 B CN115184477 B CN 115184477B CN 202210450343 A CN202210450343 A CN 202210450343A CN 115184477 B CN115184477 B CN 115184477B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 33
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 32
- 150000002170 ethers Chemical class 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 14
- 239000012086 standard solution Substances 0.000 claims description 14
- 150000002500 ions Chemical group 0.000 claims description 10
- 230000004044 response Effects 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000012634 fragment Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000012937 correction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 claims 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims 4
- -1 ether compound Chemical class 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000010813 internal standard method Methods 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- 238000004451 qualitative analysis Methods 0.000 abstract 1
- 238000004445 quantitative analysis Methods 0.000 abstract 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 70
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 35
- 239000006228 supernatant Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 8
- 238000012795 verification Methods 0.000 description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraethylene glycol dimethyl ether Natural products COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
-
- 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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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention belongs to the technical field of detection, and particularly discloses a detection method of ether compounds DOL and DME in lithium-sulfur battery electrolyte. The method performs qualitative and quantitative analysis on the ether compound in the lithium-sulfur battery electrolyte by using a gas chromatograph-mass spectrometer, reduces instrument errors by adopting an internal standard method, and has the advantages of small sample consumption, high detection speed, simple operation, high accuracy and the like. Meanwhile, before analyzing the sample, lithium in the electrolyte is precipitated and separated, so that corrosion of the sample to be tested to the chromatographic column is effectively prevented, damage to the chromatographic column is reduced, replacement frequency of the chromatographic column is reduced, and equipment maintenance cost is saved.
Description
Technical Field
The invention belongs to the technical field of quantitative detection, and particularly relates to a detection method of an ether compound in lithium-sulfur battery electrolyte.
Background
The lithium sulfur battery has the characteristics of low price, high energy density, long cycle life, environmental friendliness and the like, and becomes a research hot spot in the field of global secondary batteries. The electrolyte is an important component of the lithium-sulfur battery, plays a role in transmitting charge between the anode and the cathode in the battery, and is important to the specific capacity, the working temperature range, the cycle efficiency, the safety performance and the like of the battery.
The solvent is used as the basis of the battery electrolyte system, and the solubility of lithium salt, additives, intermediates in charge and discharge processes and the like is related to the battery performance. Among the most commonly used solvents in lithium sulfur batteries are ether solvents such as 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), tetra (ethylene glycol) dimethyl ether (teggme, G4), and the like. DME is a polar solvent with high polysulfide solubility, but also readily reacts with metallic lithium negative electrodes; DOL has a lower solubility for polysulfides, but contributes to the formation of a more stable SEI film on the surface of a lithium anode. Due to the synergistic effect of DOL and DME, the lithium sulfur battery prepared from the DOL/DME mixed solvent based electrolyte exhibits the best capacity retention and longer cycle life.
In scientific research practice, it is found that the electrolyte of the lithium-sulfur battery can decompose in the long-term circulation process, and the battery capacity can be fluctuated sharply when the electrolyte is consumed to a certain extent, so that the service life of the battery is terminated. The simple and rapid detection method for the ether compound content in the lithium sulfur battery electrolyte is researched, and has great significance for the loss process, failure mechanism and the like of the lithium sulfur battery electrolyte.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a simple and rapid detection method for ether compounds DOL and DME in lithium-sulfur battery electrolyte.
In order to achieve the above object, the present invention provides the following technical solutions.
The method for detecting the ether compounds DOL and DME in the lithium sulfur battery electrolyte comprises the following steps:
Step S1, determining fragment ion signal peaks of a compound to be tested:
Preparing detection liquid consisting of pure DOL, DME, an internal standard compound and a solvent A;
Using a SCAN mode of GCMS (gas chromatography-mass spectrometer) to qualitatively analyze the compounds of the detection liquid, and determining fragment ion signal peaks of DOL, DME and internal standard compounds;
Step S2, establishing a response relation between the compound concentration and the GCMS:
Preparing a plurality of standard solutions, wherein DOL and DME concentrations in the plurality of standard solutions are different, but the concentrations of internal standard compounds are the same;
Detecting standard liquid by adopting a SIM mode of GCMS, integrating the strongest peak areas of DOL and DME in a plurality of standard liquids and internal standard compounds, drawing standard curves of the concentration and peak area of the DOL and DME, and determining a relation equation of the concentration and the peak area by utilizing an internal standard correction curve;
step S3, measuring ether compounds DOL and DME in the lithium sulfur battery electrolyte:
Dissolving electrolyte to be measured in a solvent C, adding an internal standard compound, and uniformly mixing to obtain a sample to be measured; precipitating and separating lithium in a sample to be detected, and extracting to obtain a solution to be detected;
Detecting by adopting a SIM mode of GCMS, integrating the strongest peak areas of DOL and DME in the solution to be detected, correcting instrument errors by an internal standard, and calculating the concentration of the ether compound by utilizing the equation determined in the step S2.
In step S2, since the concentrations of the internal standard compounds in the plurality of standard solutions are the same, the relationship between the concentration of the internal standard compound and the peak area should be constant.
In a preferred embodiment of the present invention, the solvent a in step S1, the solvent B in the standard solution in step S2, the solvent C in step S3, and the extractant for extraction in step S3 are the same, preferably cyclohexane.
In a preferred embodiment of the invention, the internal standard compound is n-nonane.
In a part of the preferred embodiments of the present invention, a saturated sodium carbonate solution is selected for precipitation separation of lithium from the sample to be tested.
According to the technical scheme, the ether compound in the lithium-sulfur battery electrolyte is qualitatively and quantitatively analyzed through the gas chromatography-mass spectrometer, and an internal standard method is adopted to reduce instrument errors, so that the method has the advantages of being small in sample consumption, high in detection speed, simple to operate, high in accuracy and the like. Because lithium in the electrolyte can corrode the chromatographic column, the lithium in the electrolyte is precipitated and separated before the sample is analyzed, so that the corrosion of the sample to be detected to the chromatographic column is effectively prevented, the damage to the chromatographic column is reduced, the replacement frequency of the chromatographic column is reduced, and the equipment maintenance cost is saved.
Drawings
FIG. 1 is a full spectrum scan of a test solution in an example.
FIG. 2 is a mass spectrum of DME, DOL and n-nonane.
FIG. 3 shows the detection patterns of the standard solutions in the examples, wherein a is the detection pattern of the standard solution with DOL and DME concentrations of 250ppm, b is the detection pattern of the standard solution with DOL and DME concentrations of 750ppm, c is the detection pattern of the standard solution with DOL and DME concentrations of 1250ppm, and d is the detection pattern of the standard solution with DOL and DME concentrations of 1750 ppm.
FIG. 4 is a graph of DME versus DOL response versus concentration, wherein a is the graph of DME response versus concentration, and b is the graph of DOL response versus concentration.
FIG. 5 is a diagram of the detection of the solution to be tested in the example.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
In a preferred embodiment of the present invention:
Detecting ether compounds DOL and DME in the lithium-sulfur battery electrolyte by using a gas chromatography-mass spectrometer, wherein the chromatographic conditions are as follows: the detection chromatographic column is a fused quartz capillary column of inner coating polyethylene glycol (PEG), the column length is 30m, the inner diameter is 0.25 mm, the thickness of the inner coating is 0.25 mu m, the carrier gas is high-purity helium, the carrier gas flow is 1.44 mL/min, the purging flow is 6 mL/min, the split ratio is 15:1, and the sample inlet temperature is 200 ℃; the sample volume was 1. Mu.L, the column temperature was set at 45℃and maintained at 3 min ℃by programmed heating, then at 10℃/min to 100℃and at 20℃/min to 230 ℃. The mass spectrum conditions are as follows: the ion source adopts an electron bombardment ionization mode, the temperature of the ion source is 220 ℃, and the interface temperature is 230 ℃. The ion detection mass-to-charge ratios were 43, 85, 57, 45, 60, 90, 73, 44, 29, and the solvent delay time was 1.5 min.
The detection is carried out by adopting the following steps:
1) Preparing a detection liquid: and (3) transferring 5 mu L of pure DOL, DME and n-nonane to be detected by using a liquid transfer device, adding 1 mL cyclohexane for dilution, and finally oscillating 3 min by using a vortex mixer for uniform dilution to obtain detection liquid. 200 mu L of detection liquid is measured in a sample injection bottle.
2) And (3) qualitatively analyzing ether electrolyte and other organic components in the detection liquid by using a SCAN mode in GCMS. FIG. 1 is a graph showing the separation effect under full spectrum scanning of a detection liquid, wherein the ordinate represents the ionic strength and the abscissa represents the retention time.
3) The results of similarity search are shown in fig. 2, and the ion fragment types of each substance are determined as shown in table 1.
TABLE 1 ion fragmentation information
The m/z is the mass-to-charge ratio, which is an important parameter in mass spectrometry, and the radius r of an arc track formed by ions with different m/z values is in direct proportion to the m/z under certain acceleration voltage V and certain magnetic field strength E.
4) Diluting the electrolyte: the lithium sulfur electrolyte (DOL to DME volume ratio in the electrolyte is 1:1) was removed by a pipette 10, 30, 50, 70. Mu.L, respectively, and added to a glass bottle filled with 20mL cyclohexane, and shaken for 10min using a vortex mixer, and allowed to stand for half an hour.
5) And (3) preparing an internal standard: accurately weighing 12.5 mu L of n-nonane, adding into a glass bottle containing 10 mL cyclohexane, shaking 10 min by using a vortex mixer, and standing for half an hour. (frozen and sealed in refrigerator after each use, and prepared once in two weeks).
6) Preparing standard liquid: accurately measuring 10 mu L of diluted electrolyte and 10 mu L of internal standard respectively, and adding the diluted electrolyte and the internal standard into a 1# 4 centrifuge tube filled with 0.5mL saturated sodium carbonate respectively; oscillating 3 min using a vortex mixer to precipitate lithium salt and lithium nitrate; adding 0.5mL cyclohexane into a 1-4 # centrifuge tube, oscillating 3 min by using a vortex mixer, performing ultrasonic treatment for 15min to extract DOL and DME, accurately measuring 400 mu L of supernatant into a 5-8 # centrifuge tube by using a pipette, adding the supernatant of the 1# centrifuge tube into the 5# centrifuge tube, adding the supernatant of a 2# centrifuge tube into a 6# centrifuge tube, adding the supernatant of the 3# centrifuge tube into a 7# centrifuge tube, and adding the supernatant of the 4# centrifuge tube into an 8# centrifuge tube; adding 0.5mL cyclohexane into the 1-4 # centrifuge tube again, oscillating 3 min on a vortex mixer, performing ultrasonic treatment for 15min, accurately measuring 400 mu L of supernatant in the 5-8 # centrifuge tube by using a liquid-transferring gun after standing, adding the supernatant of the 1# centrifuge tube into the 5# centrifuge tube, adding the supernatant of the 2# centrifuge tube into the 6# centrifuge tube, adding the supernatant of the 3# centrifuge tube into the 7# centrifuge tube, and adding the supernatant of the 4# centrifuge tube into the 8# centrifuge tube; and finally, centrifuging the liquid to be detected in the 5-8 # centrifuge tube at the rotating speed of 12000 r/min for 10 min in a centrifuge, and respectively transferring 200 mu L of supernatant into four sample injection bottles to obtain standard liquid.
7) Standard solution detection and analysis: standard solutions in sample bottles were tested using the SIM monitoring mode of SCMS, and the results are shown in figure 3. The strongest peaks of the respective substances in fig. 3 were integrated, and table 2 shows the correspondence between the concentration of each substance and the integrated area. Drawing a curve of the concentration of a substance in a standard solution and the integral area, and fitting a curve equation by using a least square method to obtain a curve of the relation (y) between the response value (x (integral area/1000)) of DME and DOL and the concentration, wherein the curve is shown in figure 4, and the equation is that
DME: y=4.15x-115.55 r=0.9997
DOL: y=10.06x-70.95 r=0.9992
TABLE 2 DOL correspondence between DME and n-nonane concentrations and integrated area
8) Treating a sample to be tested: the method comprises the steps of nondestructive disassembly of a battery in a glove box, uniformly soaking all parts in a glass bottle filled with 20mL of cyclohexane, shaking uniformly, and standing for 12 hours to obtain a solution A; accurately measuring 10 mu L of the solution A and 10 mu L of the internal standard respectively, and adding the solution A and the internal standard into a 9# centrifuge tube filled with 0.5 mL saturated sodium carbonate; oscillating 3 min using a vortex mixer to precipitate lithium salt and lithium nitrate; adding 0.5 mL cyclohexane into the centrifuge tube, oscillating 3 min by using a vortex mixer, performing ultrasonic treatment for 15min to extract DOL and DME, and accurately measuring 400 mu L of supernatant in a 10# centrifuge tube by using a pipette; adding 0.5 mL cyclohexane into the 9# centrifuge tube again, oscillating 3 min on a vortex mixer, performing ultrasonic treatment for 15min, and accurately measuring 400 mu L of supernatant in the 10# centrifuge tube by using a pipette after standing; and finally centrifuging the 10# centrifuge tube in a centrifuge at a rotation speed of 12000 r/min for 10min, and transferring 200 mu L of supernatant into a sample injection bottle to obtain the solution to be tested.
9) Detecting a solution to be detected: the solution to be tested was tested using the SIM monitoring mode of GCMS, the results are shown in fig. 5.
10 Analysis of the detection results: the strongest peaks of each of the compounds in fig. 5 were integrated, substituted into the fitted equation and corrected using internal standards. The calculated detection results are shown in table 3.
TABLE 3 calculation of substance concentration
And (3) verifying a detection result:
And 9mL of the solution to be tested obtained in the step 8) and 1mL of the sample with known concentration are removed to obtain a verification solution. And according to the detection result. Step 8) the DME concentration in the test solution is 1933.54ppm and the DOL concentration is 1604.78ppm; the concentration of DME in the sample of known concentration is 2500ppm and the concentration of DOL is 2500ppm.
Accurately measuring 10 mu L of verification solution and 10 mu L of internal standard prepared in the step 5) respectively, adding the verification solution and the internal standard into a11 # centrifuge tube filled with 0.5 mL saturated sodium carbonate, and oscillating 3 min by using a vortex mixer to precipitate lithium salt and lithium nitrate; adding 0.5 mL cyclohexane into the 11# centrifuge tube, oscillating 3 min by using a vortex mixer, and performing ultrasonic treatment for 15min to extract DOL and DME; accurately measuring 400 mu L of supernatant into a 12# centrifuge tube by using a pipette; adding 0.5 mL cyclohexane into the 11# centrifuge tube again, oscillating 3: 3 min on a vortex mixer, performing ultrasonic treatment for 15min, standing, and accurately measuring 400 mu L of supernatant into the 12# centrifuge tube by using a pipette; and finally centrifuging the solution in the 12 centrifuge tubes in a centrifuge at a rotation speed of 12000 r/min for 10 min, and transferring 200 mu L of supernatant into a sample injection bottle to obtain the verification solution to be detected.
The verification solution to be tested was tested using the SIM monitoring mode of GCMS, the results are shown in fig. 5.
The strongest peaks of each DOL and DME were integrated, substituted into the fitted equation, and corrected using an internal standard, with the following results.
TABLE 4 concentration verification results
The detection analysis and verification process can find that the method for detecting the ether compounds DOL and DME in the lithium sulfur battery electrolyte can well detect the ether solvents DOL and DME in the electrolyte, and has higher accuracy.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. The method for detecting the ether compounds DOL and DME in the lithium sulfur battery electrolyte is characterized by comprising the following steps of:
Step S1, determining fragment ion signal peaks of a compound to be tested:
preparing detection liquid consisting of pure DOL, DME, an internal standard compound and cyclohexane; the internal standard compound is n-nonane;
using a SCAN mode of GCMS to qualitatively analyze the compounds of the detection solution, and determining fragment ion signal peaks of DOL, DME and an internal standard compound;
Step S2, establishing a response relation between the compound concentration and the GCMS:
Preparing a plurality of standard solutions, wherein DOL and DME concentrations in the plurality of standard solutions are different, but the concentrations of internal standard compounds are the same;
Detecting standard liquid by adopting a SIM mode of GCMS, integrating the strongest peak areas of DOL and DME in a plurality of standard liquids and internal standard compounds, drawing standard curves of the concentration and peak area of the DOL and DME, and determining a relation equation of the concentration and the peak area by utilizing an internal standard correction curve;
step S3, measuring ether compounds DOL and DME in the lithium sulfur battery electrolyte:
dissolving electrolyte to be measured in cyclohexane, adding an internal standard compound n-nonane, and uniformly mixing to obtain a sample to be measured; precipitating and separating lithium in a sample to be detected, and extracting by using an extractant cyclohexane to obtain a solution to be detected;
Detecting by adopting a SIM mode of GCMS, integrating the strongest peak areas of DOL and DME in the solution to be detected, correcting instrument errors by an internal standard, and calculating the concentration of the ether compounds DOL and DME by utilizing the equation determined in the step S2.
2. The method for detecting ether compounds DOL and DME in lithium-sulfur battery electrolyte as defined in claim 1, wherein the method is characterized in that saturated sodium carbonate solution is selected for precipitation and separation of lithium in a sample to be detected.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104792901A (en) * | 2015-05-06 | 2015-07-22 | 哈尔滨工业大学 | Quantitative measuring method of lithium ion battery electrolyte solvent |
| CN113376304A (en) * | 2021-06-02 | 2021-09-10 | 万向一二三股份公司 | Method for detecting carbonate organic matters and additives in lithium ion battery electrolyte by GC-MS (gas chromatography-mass spectrometry) |
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