Analysis method for components of photocuring polymer electrolyte and application of analysis method

Abstract

The invention provides an analysis method for components of a photocuring polymer electrolyte. The analysis method comprises the following steps: (1) performing quantitative analysis on low-boiling-point substances in the photocuring polymer electrolyte by a drying method; carrying out qualitative and quantitative analysis on low-boiling-point substances in the photocuring polymer electrolyte by adopting a gas chromatography-mass spectrometer; (2) carrying out qualitative and quantitative analysis on the polymer in the photocuring polymer electrolyte by adopting a pyrolysis gas chromatography-mass spectrometer; (3) carrying out qualitative and quantitative analysis on elements in the photocuring polymer electrolyte by adopting an X-ray fluorescence spectrometer and an inductively coupled plasma emission spectrometer; (4) performing qualitative analysis on the salt in the photocuring polymer electrolyte by adopting a nuclear magnetic resonance spectrometer; and (5) synthesizing the test results of the steps (1)-(4) to obtain the component formula of the photocuring polymer electrolyte. The analysis method can more efficiently and accurately test the specific composition of the polymer electrolyte.

Description

Technical Field

[0001] The invention belongs to the technical field of analysis and detection methods, and particularly relates to an analysis method for light-cured polymer electrolyte components and an application thereof. Background Art

[0002] Polymer electrolytes have been a research hotspot in the field of polymer materials for the past 20 years. They not only possess excellent electrical conductivity but also possess the unique characteristics of polymer materials, such as light weight, flexibility, elasticity, and easy film formation. Polymer electrolytes generally consist of a solvent, polymer, salt, and initiator. Polymer electrolytes based on polyethylene oxide (PEO) and lithium salts are currently the most studied, primarily due to their ability to form stable complexes with lithium salts in the absence of any organic plasticizers, resulting in high electrical conductivity.

[0003] With technological advancements, the use of polymer electrolytes has gradually increased, which in turn means that the amount of polymer electrolyte waste is also increasing. In line with the principles of sustainable development and green chemistry, the recycling and reuse of waste is currently a major concern. When recycling and reusing waste, since the composition of the waste is unknown, it is necessary to analyze the polymer electrolyte components to improve recycling efficiency. Furthermore, analyzing unknown electrolyte components can provide researchers with new research ideas and technical support. Therefore, accurately analyzing the content of each unknown polymer electrolyte component is of great significance for the recycling, production, and research and development of polymer electrolytes. However, existing analytical methods are complex, difficult to analyze, and have low accuracy.

[0004] Therefore, developing a simple analytical method that can accurately and comprehensively analyze the specific components of polymer electrolytes is an urgent problem to be solved in this field. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a method for analyzing the composition of a photocurable polymer electrolyte and its application. The analytical method can more efficiently and accurately test the specific composition of the polymer electrolyte.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a method for analyzing components of a photocurable polymer electrolyte, the method comprising the following steps:

[0008] (1) Quantitative analysis of low-boiling-point substances in the photocurable polymer electrolyte by a drying method; qualitative and quantitative analysis of low-boiling-point substances in the photocurable polymer electrolyte by gas chromatography-mass spectrometry;

[0009] (2) Qualitative and quantitative analysis of polymers in photocurable polymer electrolytes using pyrolysis gas chromatography-mass spectrometry;

[0010] (3) Qualitative and quantitative analysis of elements in photocurable polymer electrolytes using X-ray fluorescence spectrometer and inductively coupled plasma optical emission spectrometer;

[0011] (4) Using nuclear magnetic resonance spectroscopy to qualitatively analyze the salt in the photocurable polymer electrolyte;

[0012] (5) Combining the test results of steps (1) to (4), the composition formula of the photocurable polymer electrolyte is obtained.

[0013] In the present invention, the low-boiling-point substances in the photocurable polymer electrolyte are mainly solvents and additives, and the high-boiling-point substances are mainly polymers and lithium salts; the respective contents of the low-boiling-point substances and the high-boiling-point substances in the polymer electrolyte are determined by a drying method, and the specific composition of the low-boiling-point substances is qualitatively and quantitatively analyzed by gas chromatography; then, the high-boiling-point substances in the photocurable electrolyte can be qualitatively and quantitatively analyzed by pyrolysis gas chromatography-mass spectrometry, and based on the pyrolysis gas chromatography-mass spectrometry results, the polymer electrolyte is subjected to elemental analysis using an X-ray fluorescence spectrometer and an inductively coupled plasma emission spectrometer, and then, in combination with a nuclear magnetic resonance spectrometer, the lithium salt in the polymer electrolyte is further qualitatively analyzed. The analytical method can quickly, efficiently and accurately obtain the components of an unknown polymer electrolyte.

[0014] Preferably, the drying method in step (1) comprises: weighing the photocurable polymer electrolyte to obtain the mass of the photocurable polymer electrolyte before drying; then drying the photocurable polymer electrolyte at 100-200°C (for example, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, etc.) for 4-8h (for example, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, etc.), weighing, and obtaining the mass of the photocurable polymer electrolyte after drying, thereby obtaining the content of low-boiling-point substances and high-boiling-point substances in the photocurable polymer electrolyte.

[0015] In the present invention, 1 to 5 g of sample is weighed during drying, and the percentage of volatile substances (ie, low-boiling-point substances) in the polymer electrolyte can be obtained based on the mass change of the polymer electrolyte before and after drying.

[0016] Preferably, the test conditions of the gas chromatography-mass spectrometer in step (1) are as follows.

[0017] Inlet temperature: 280-300°C; for example, it can be 280°C, 285°C, 290°C, 295°C, 300°C, etc.; carrier gas: helium; flow rate: 0.5-1.5mL / min, for example, it can be 0.5mL / min, 0.6mL / min, 0.7mL / min, 0.8mL / min, 0.9mL / min, 1mL / min, 1.1mL / min, 1.2mL / min, 1.3mL / min, 1.4mL / min, 1.5mL / min, etc.

[0018] Injection mode: split injection, the split ratio is 20-50:1, for example, 20:1, 22:1, 25:1, 28:1, 30:1, 32:1, 35:1, 38:1, 40:1, 42:1, 44:1, 46:1, 48:1, 50:1, etc.

[0019] Injection concentration: 0.05-0.2 g / mL, for example, 0.05 g / mL, 0.06 g / mL, 0.08 g / mL, 0.1 g / mL, 0.12 g / mL, 0.14 g / mL, 0.16 g / mL, 0.18 g / mL, 0.2 g / mL, etc.

[0020] In the present invention, when a gas chromatograph-mass spectrometer is used for testing, the sample is original and has not been processed in any way. Before the test, the sample is mixed with a solvent to prepare a sample of a specific concentration, and then filtered through a 0.22 μm nylon filter head before the sample is tested. The solvent includes a mixed solvent of methanol and chloroform.

[0021] Heating program: Heating program A or Heating program B; the heating program A comprises: maintaining the temperature at 30-50°C (for example, 30°C, 32°C, 34°C, 36°C, 38°C, 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, etc.) for 1-5 min (for example, 1 min, 2 min, 3 min, 4 min, 5 min, etc.), and then heating the temperature at a rate of 6-14°C / min (for example, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min, 11°C / min, 12°C / min, 13°C / min, 14°C / min, etc.) to 120-16 After the temperature is increased from 0°C (for example, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, etc.), the temperature is increased at a rate of 12-26°C / min (for example, 12°C / min, 13°C / min, 14°C / min, 15°C / min, 16°C / min, 17°C / min, 18°C / min, 19°C / min, 20°C / min, 21°C / min, 22°C / min, 23°C / min, 24°C / min, 25°C / min, 26°C / min, etc.) to 280-310°C (for example, 280°C, 290°C, etc.) , 300°C, 310°C, etc.); the heating program B includes: maintaining at 30-50°C (for example, 30°C, 32°C, 34°C, 36°C, 38°C, 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, etc.) for 1-5 min (for example, 1 min, 2 min, 3 min, 4 min, 5 min, etc.), and then heating at 2-8°C / min (for example, 2°C / min, 2.5°C / min, 3°C / min, 3.5°C / min, 4°C / min, 4.5°C / min, 5°C / min, 5.5°C / min, 6°C / min, 6.5°C / min, 7°C / min, The temperature is then raised to 100-140°C (for example, 100°C, 102°C, 105°C, 108°C, 110°C, 112°C, 115°C, 118°C, 120°C, 122°C, 125°C, 128°C, 130°C, 132°C, 135°C, 138°C, 140°C, etc.), and then the temperature is raised to 100-140°C (for example, 100°C, 102°C, 105°C, 108°C, 110°C, 112°C, 115°C, 118°C, 120°C, 122°C, 125°C, 128°C, 130°C, 132°C, 135°C, 138°C, 140°C, etc.), and then the temperature is raised to 100-140°C (for example, 10The temperature is then raised at a rate of 5°C / min, 15°C / min, etc. to 180-240°C (for example, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, etc.), and then raised at a rate of 20-25°C / min (for example, 20°C / min, 20.5°C / min, 21°C / min, 21.5°C / min, 22°C / min, 22.5°C / min, 23°C / min, 23.5°C / min, 24°C / min, 24.5°C / min, 25°C / min, etc.) to 280-310°C (for example, 280°C, 285°C, 290°C, 295°C, 300°C, 305°C, 310°C, etc.).

[0022] Ion source temperature: 220-240°C, for example, 220°C, 225°C, 230°C, 235°C, 240°C, etc., more preferably 230°C.

[0023] Interface temperature: 290-310°C, for example, 290°C, 295°C, 300°C, 305°C, 310°C, etc., more preferably 310°C.

[0024] Ionization mode: electron bombardment 70eV.

[0025] Collection time: 1 to 28 minutes.

[0026] Scan range: 29-600 m / z.

[0027] In the present invention, the chromatographic column of the gas chromatograph is a DB-1701 chromatographic column.

[0028] Preferably, the test conditions of the pyrolysis gas chromatography mass spectrometer in step (2) are as follows.

[0029] Cracking temperature: 400-800°C, for example, it can be 400°C, 420°C, 440°C, 460°C, 480°C, 500°C, 520°C, 540°C, 560°C, 580°C, 600°C, 620°C, 640°C, 660°C, 680°C, 700°C, 720°C, 740°C, 760°C, 780°C, 800°C, etc.; Cracking time: 0.1-0.3 min, for example, it can be 0.1 min, 0.12 min, 0.14 min, 0.16 min, 0.18 min, 0.2 min, 0.22 min, 0.24 min, 0.26 min, 0.28 min, 0.3 min, etc.

[0030] Inlet temperature: 200-300°C, for example, 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, etc.; carrier gas: helium; flow rate: 0.5-1.5 mL / min, for example, 0.5 mL / min, 0.6 mL / min, 0.7 mL / min, 0.8 mL / min, 0.9 mL / min, 1 mL / min, 1.1 mL / min, 1.2 mL / min, 1.3 mL / min, 1.4 mL / min, 1.5 mL / min, etc.

[0031] Injection mode: split injection, the split ratio is 20-50:1, for example, 20:1, 22:1, 25:1, 28:1, 30:1, 32:1, 35:1, 38:1, 40:1, 42:1, 44:1, 46:1, 48:1, 50:1, etc.

[0032] Heating program: Heating program C or Heating program D; the heating program C includes: maintaining at 30-50°C (for example, 30°C, 32°C, 34°C, 36°C, 38°C, 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, etc.) for 2-4 min (for example, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, 5 min, etc.), and then heating at a rate of 6-14°C / min (for example, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min, 11°C / min, 12°C / min, 13°C / min, 14°C / min, etc.) to 120-160°C ℃ (for example, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, etc.), and then increase the temperature to 280℃-310℃ (for example, 280℃, 290℃, 300℃, 310℃, etc.) at a heating rate of 15-25℃ / min (for example, 15℃ / min, 16℃ / min, 17℃ / min, 18℃ / min, 19℃ / min, 20℃ / min, 21℃ / min, 22℃ / min, 23℃ / min, 24℃ / min, 25℃ / min, etc.); the heating program D includes: 30℃-50℃ (for example, 30℃, 32℃, 34℃, 36℃, After the temperature is maintained at 38°C, 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, etc. for 1-5 min (for example, 1 min, 2 min, 3 min, 4 min, 5 min, etc.), the temperature is increased to 80-110°C (for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, etc.) at a heating rate of 1-5°C / min (for example, 1°C / min, 1.5°C / min, 2°C / min, 2.5°C / min, 3°C / min, 3.5°C / min, 4°C / min, 4.5°C / min, 5°C / min, etc.), and then the temperature is increased to 80-110°C (for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, etc.) at a heating rate of 10-15°C / min (for example, 10°C / min, 10.5 ℃ / min, 11℃ / min, 11.5℃ / min, 12℃ / min, 12.5℃ / min, 13℃ / min, 13.5℃ / min, 14℃ / min, 14.5℃ / min, 15℃ / min, etc.) to 140-170℃ (for example, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, etc.), and then heated at 20-25℃ / min (for example, 20℃ / min, 20.5℃ / min, 21℃ / min, 21.5℃ / min, 22℃ / min, 22.5℃ / min, 23℃ / min, 23.5℃ / min, 24℃ / min, 24.The temperature is raised to 280-310°C (for example, 280°C, 285°C, 290°C, 295°C, 300°C, 305°C, 310°C, etc.) at a heating rate of 5°C / min, 25°C / min, etc.

[0033] Ion source temperature: 210-250°C, for example, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, etc., more preferably 230°C.

[0034] Interface temperature: 290-310°C, for example, 290°C, 295°C, 300°C, 305°C, 310°C, etc., more preferably 310°C.

[0035] Ionization mode: electron bombardment 70eV.

[0036] Collection time: 1 to 28 minutes.

[0037] Scan range: 29-600 m / z.

[0038] The pyrolysis mode of a polymer depends on its molecular structure, so the small molecules of the fragments obtained by pyrolysis can be analyzed to qualitatively characterize the polymer in the sample; in the present invention, the sample tested by the pyrolysis gas chromatography-mass spectrometer is a solid, i.e., it does not contain volatile substances, and the original sample is dried before testing.

[0039] Preferably, the test conditions of the X-ray fluorescence spectrometer in step (3) are as follows.

[0040] Target material: power ≤ 4kW; including at least one of rhodium target, cobalt target or chromium target.

[0041] Atmosphere: vacuum.

[0042] Tube voltage: 20-40 kV, for example, 20 kV, 22 kV, 24 kV, 26 kV, 28 kV, 30 kV, 32 kV, 34 kV, 36 kV, 38 kV, 40 kV, etc., more preferably 25-35 kV.

[0043] Tube current: 50-150mA, for example, it can be 50mA, 55mA, 60mA, 65mA, 70mA, 75mA, 80mA, 85mA, 90mA, 95mA, 100mA, 105mA, 110mA, 115mA, 120mA, 125mA, 130mA, 135mA, 140mA, 145mA, 150mA, etc., and more preferably 80-120mA.

[0044] Spectral crystal: RX26.

[0045] Scanning range: 72.02°~78.02°, scanning step: 0.01~0.08°, for example, it can be 0.01°, 0.02°, 0.03°, 0.04°, 0.05°, 0.06°, 0.07°, 0.08°, etc., scanning speed: 2~20° / min, for example, it can be 2° / min, 3° / min, 4° / min, 5° / min, 6° / min, 7° / min, 8° / min, 9° / min, 10° / min, 11° / min, 12° / min, 13° / min, 14° / min, 15° / min, 16° / min, 17° / min, 18° / min, 19° / min, 20° / min, etc.

[0046] Preferably, the scanning step length of the X-ray fluorescence spectrometer is 0.04-0.06°, and the scanning speed is 5-15° / min.

[0047] Preferably, the test conditions of the inductively coupled plasma emission spectrometer in step (3) are as follows.

[0048] Plasma RF power: 1000-1500 W, for example, 1000 W, 1020 W, 1050 W, 1080 W, 1100 W, 1120 W, 1150 W, 1180 W, 1200 W, 1220 W, 1250 W, 1280 W, 1300 W, 1320 W, 1350 W, 1380 W, 1400 W, 1420 W, 1450 W, 1480 W, 1500 W, etc.

[0049] Working gas: argon gas, the purity of the argon gas is ≥99.999%.

[0050] Plasma gas flow rate: 8-15 L / min, for example, 8 L / min, 8.2 L / min, 8.4 L / min, 8.6 L / min, 8.8 L / min, 9 L / min, 9.2 L / min, 9.4 L / min, 9.6 L / min, 9.8 L / min, 10 L / min, 10.2 L / min, 10.4 L / min, 10.6 L / min, 10.8 L / min, 11 L / min, 11.2 L / min n, 11.4L / min, 11.6L / min, 11.8L / min, 12L / min, 12.2L / min, 12.4L / min, 12.6L / min, 12.8L / min, 13L / min , 13.2L / min, 13.4L / min, 13.6L / min, 13.8L / min, 14L / min, 14.2L / min, 14.6L / min, 14.8L / min, 15L / min, etc.

[0051] Auxiliary gas flow rate: 0.9-1.1 L / min, for example, it can be 0.9 L / min, 0.92 L / min, 0.94 L / min, 0.96 L / min, 0.98 L / min, 1 L / min, 1.02 L / min, 1.04 L / min, 1.06 L / min, 1.08 L / min, 1.1 L / min, etc.

[0052] Atomizer gas flow rate: 0.6-0.8 L / min, for example, it can be 0.6 L / min, 0.61 L / min, 0.62 L / min, 0.63 L / min, 0.64 L / min, 0.65 L / min, 0.66 L / min, 0.67 L / min, 0.68 L / min, 0.69 L / min, 0.7 L / min, 0.71 L / min, 0.72 L / min, 0.73 L / min, 0.74 L / min, 0.75 L / min, 0.76 L / min, 0.77 L / min, 0.78 L / min, 0.79 L / min, 0.8 L / min, etc.

[0053] The rotation speed of the peristaltic pump is 10 to 15 rpm, for example, it can be 10 rpm, 11 rpm, 12 rpm, 13 rpm, 14 rpm, 15 rpm, etc.

[0054] In the present invention, by using an X-ray fluorescence spectrometer (XRF) in conjunction with an inductively coupled plasma emission spectrometer (ICP), the elements in the polymer electrolyte can be accurately and comprehensively obtained to avoid missed detections; among them, ICP can quantitatively obtain the lithium salt composition in the polymer electrolyte.

[0055] Preferably, the plasma radio frequency power of the inductively coupled plasma optical emission spectrometer is 1200-1400W.

[0056] Preferably, the nebulizer gas flow rate of the inductively coupled plasma optical emission spectrometer is 0.68 to 0.75 L / min.

[0057] Preferably, the test conditions of the nuclear magnetic resonance spectrometer in step (4) are as follows.

[0058] Pulse sequence: zg pulse sequence.

[0059] Spectral width: 200~300HZ.

[0060] Center point -20~-50ppm.

[0061] Resonance frequency: 376.48HZ.

[0062] Sampling times: 16 to 32 times.

[0063] Acquisition time: 2 to 10 seconds.

[0064] Relaxation time: 10~20s.

[0065] In the present invention, a nuclear magnetic resonance spectrometer is used to perform qualitative analysis on the lithium salt in the polymer electrolyte, and further combined with XRF and ICP data, the composition and content of the lithium salt in the polymer electrolyte can be accurately obtained.

[0066] In a second aspect, the present invention provides an application of the analytical method according to the first aspect in polymer electrolyte production, polymer electrolyte recovery, and polymer electrolyte research and development.

[0067] The numerical range described in the present invention includes not only the point values listed above, but also any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.

[0068] Compared with the prior art, the present invention has the following beneficial effects:

[0069] The present invention provides a method for analyzing the components of a photocurable polymer electrolyte. The method determines the respective contents of low-boiling-point substances and high-boiling-point substances in the polymer electrolyte by a drying method, and performs qualitative and quantitative analysis on the specific composition of the low-boiling-point substances by gas chromatography. A pyrolysis gas chromatography-mass spectrometer is then used to perform qualitative and quantitative analysis on the high-boiling-point substances in the photocurable electrolyte. Based on the pyrolysis gas chromatography-mass spectrometry results, an X-ray fluorescence spectrometer and an inductively coupled plasma emission spectrometer are used to perform elemental analysis on the polymer electrolyte. Then, a nuclear magnetic resonance spectrometer is used to further characterize the lithium salt in the polymer electrolyte. The analytical method can rapidly, efficiently, and accurately obtain the components of an unknown polymer electrolyte, and is of great significance for the recovery, production, and research and development of polymer electrolytes. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 This is a gas chromatography-mass spectrum of low-boiling-point substances in the photocurable polymer electrolyte obtained by the analysis method provided in Example 1 of the present invention.

[0071] Figure 2 This is a pyrolysis gas chromatography mass spectrum of the polymer in the photocurable polymer electrolyte obtained by the analysis method provided in Example 1 of the present invention.

[0072] Figure 3 This is the nuclear magnetic resonance spectrum of the photocurable polymer electrolyte obtained by the analysis method provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0073] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0074] The materials and instruments used in the present invention are as follows:

[0075] Photocurable polymer electrolyte: commercially available.

[0076] Gas chromatograph-mass spectrometer: Agilent 8860-5977B.

[0077] Pyrolysis gas chromatography-mass spectrometer: The pyrolysis device model is EGA-PY-3030D, and the gas chromatography-mass spectrometer equipment model is: GCMS-QP2020NX.

[0078] X-ray fluorescence spectrometer: Rigaku ZSX PrimusIII+.

[0079] Inductively coupled plasma optical emission spectrometer: Agilent 5800.

[0080] NMR spectrometer: Bruker AVANCE NEO 400 MHz.

[0081] Example 1

[0082] This embodiment provides a method for analyzing the composition of a photocurable polymer electrolyte, which specifically includes the following steps:

[0083] (1) Take a glass dish and weigh it to obtain a mass of 28.1797 g; then take a certain amount of photocurable polymer electrolyte sample into the glass dish, weigh the total mass of the glass dish and the sample to be 30.1987 g, and obtain the mass of the sample before drying to be 2.019 g; then place the glass dish containing the sample in an oven at a temperature of 100°C and dry it for 4 hours, weigh the total mass of the glass dish and the sample after drying to be 29.2598 g, and obtain the content of low-boiling-point substances to be 0.9389 g, thereby obtaining the mass percentage of low-boiling-point substances (solvents, additives, etc.) in the photocurable polymer electrolyte to be 46.5%, and the mass percentage of high-boiling-point substances (polymer and lithium salt) to be 53.5%.

[0084] (2) 0.1 g of photocurable polymer electrolyte was dissolved in 1 mL of a mixed solvent of methanol and chloroform in a volume ratio of 1:1, filtered with a 0.22 μm nylon filter, loaded, and subjected to qualitative and quantitative analysis using a gas chromatography-mass spectrometer. The specific test conditions were as follows: chromatographic column: DB-1701; inlet temperature: 300 °C; carrier gas: helium, flow rate: 1 mL / min, split ratio: 40:1; heating program: initial temperature: 40 °C for 3 min, then heated to 140 °C at a rate of 10 °C / min, and then heated to 300 °C at a rate of 20 °C / min; ion source temperature: 230 °C, interface temperature: 310 °C, ionization mode: electron bombardment (70 eV), acquisition time: 1 to 28 min, scanning range: 29 to 600 m / z.

[0085] The test results of the gas chromatography mass spectrometer are as follows Figure 1 As shown, by comparing with the NIST spectral library, it can be seen that the low-boiling-point substances in the photocurable electrolyte are hexyl acetate, glycidyl methacrylate, cyclohexyl acrylate, tetraethylene glycol diacrylate and 2-hydroxy-2-methylpropiophenone; then, by normalizing the integrated area of the characteristic peaks of the substances and combining it with the total mass of the low-boiling-point substances obtained in step (1), the content of each substance can be obtained.

[0086] (3) Take 0.3 mg of the dried sample in step (1) and place it in a pyrolysis dish, and use a pyrolysis gas chromatography-mass spectrometer to perform qualitative and quantitative analysis of the polymer in the polymer electrolyte. The specific test conditions are: pyrolysis temperature is 600°C, pyrolysis time is 0.2 min; chromatographic column is: DB-1701, inlet temperature: 300°C, carrier gas: helium, flow rate: 1 mL / min, split ratio: 40:1; heating program: initial temperature: 40°C for 3 min, then increase the temperature to 140°C at 10°C / min, and then increase the temperature to 300°C at 20°C / min; ion source temperature: 230°C, interface temperature: 310°C, ionization mode: electron bombardment (70 eV), acquisition time: 1 to 28 min, scanning range: 29 to 600 m / z.

[0087] The pyrolysis gas chromatography mass spectrometer test results are as follows Figure 2 As shown; by comparing with the NIST spectral library, the spectrum showed the cracking fragments of 1,4-dioxane, diethylene glycol butyl ether, ethylene oxide, and (2-ethoxy-1-methoxyethoxy)ethylene, which means that the polymer in the sample is qualitatively identified as polyethylene oxide. At the same time, the spectrum showed the cracking fragments of lithium bis(trifluoromethanesulfonyl imide), which means that the sample contains lithium bis(trifluoromethanesulfonyl imide). Subsequent XRF and ICP tests can further identify and quantify the salts.

[0088] (4) X-ray fluorescence spectrometer was used to qualitatively analyze the elements in the original sample of photocurable polymer electrolyte. The specific test conditions were as follows: target material: 4kW rhodium target; atmosphere: vacuum; tube voltage: 30kV, tube current: 100mA; spectrometer crystal: RX26; scanning range: 72.02°~78.02°, scanning step: 0.05°, scanning speed: 10° / min.

[0089] The X-ray fluorescence spectrometer test results are shown in Table 1. According to the X-ray fluorescence spectrometer test results, the polymer electrolyte contains S and F, which is consistent with the pyrolysis gas chromatography mass spectrometer test results.

[0090] (5) Inductively coupled plasma emission spectrometry was used to further test and analyze the elements in the original sample of the photocurable polymer electrolyte. The specific test conditions were as follows: the plasma RF power was 1300 W; the working gas was high-purity argon with a purity of 99.999%; the plasma gas flow rate was 12 L / min; the auxiliary gas flow rate was 1 L / min; the atomizer gas flow rate was 0.72 L / min; and the peristaltic pump speed was 15 rpm.

[0091] The test results using inductively coupled plasma optical emission spectrometry are shown in Table 2. According to the results of the inductively coupled plasma optical emission spectrometry, the photocurable polymer electrolyte contains S and Li. Combined with XRF, it can be known that the salt in the photocurable polymer electrolyte is a lithium salt containing F and S.

[0092] (6) According to the test results of steps (3), (4) and (5), the type of fluorine-containing lithium salt in the sample can be obtained, and then the fluorine spectrum of the nuclear magnetic resonance spectrometer is further tested to further qualitatively analyze the lithium salt. The specific test conditions are: using a zg pulse sequence, a spectrum width of 300 Hz, a center point of -50 ppm, a resonance frequency of 376.48 Hz, 32 sampling times, an acquisition time of 0.57 s, and a relaxation time of 20 s.

[0093] The test results of the nuclear magnetic resonance spectrometer are as follows Figure 3 shown by Figure 3 The chemical shift at -79.84 ppm indicates that the lithium salt is lithium bis(trifluoromethanesulfonyl imide). After the qualitative analysis, the ICP elemental analysis results can be used to quantitatively convert the lithium bis(trifluoromethanesulfonyl imide) to obtain a lithium salt content of 17.3%.

[0094] (7) Combining the above steps, the composition of the photocurable electrolyte can be obtained as shown in Table 3.

[0095] Example 2

[0096] This embodiment provides a method for analyzing the components of a photocurable polymer electrolyte. The only difference between the method and the embodiment 1 is that the heating program of the gas chromatograph-mass spectrometer in step (2) is as follows: the initial temperature is maintained at 40°C for 3 minutes, then heated to 120°C at a rate of 5°C / min, then heated to 200°C at a rate of 10°C / min, and then heated to 300°C at a rate of 20°C / min. The other steps and parameters are the same as those in the embodiment 1.

[0097] Example 3

[0098] This embodiment provides a method for analyzing the components of a photocurable polymer electrolyte. The only difference between the embodiment 1 is that the heating program of the pyrolysis gas chromatography-mass spectrometer in step (3) is as follows: the initial temperature is maintained at 40°C for 3 minutes, then the temperature is increased to 100°C at a rate of 2°C / min, then the temperature is increased to 140°C at a rate of 10°C / min, and then the temperature is increased to 300°C at a rate of 20°C / min. The other steps and parameters are the same as those in embodiment 1.

[0099] Example 4

[0100] This embodiment provides a method for analyzing the composition of a photocurable polymer electrolyte. The only difference between this method and embodiment 1 is that the drying temperature in step (1) is 200° C., and the other steps and parameters are the same as those in embodiment 1.

[0101] Example 5

[0102] This embodiment provides a method for analyzing the components of a photocurable polymer electrolyte. The only difference between this method and Example 1 is that in step (5), the plasma RF power of the inductively coupled plasma emission spectrometer is 1150 W, the auxiliary gas flow rate is 0.5 L / min, and the nebulizer gas flow rate is 0.65 L / min. The other steps and parameters are the same as those in Example 1.

[0103] Example 6

[0104] This embodiment provides a method for analyzing the components of a photocurable polymer electrolyte. The only difference between this method and Example 1 is that in step (5), the plasma RF power of the inductively coupled plasma emission spectrometer is 1450 W, the auxiliary gas flow rate is 1.5 L / min, and the nebulizer gas flow rate is 0.8 L / min. The other steps and parameters are the same as those in Example 1.

[0105] The mass content of each component in the photocurable polymer electrolyte obtained by the analytical method provided in Examples 1 to 6 was compared with the standard mass content of each component in the photocurable polymer electrolyte, and the absolute value of the error was calculated; the specific test results are shown in Table 4.

[0106] Table 1

[0107] element result Detection limit Elemental spectral lines F 40.6855wt% 0.25551 F-KA S 59.3145wt% 0.01583 S-KA

[0108] Table 2

[0109] Test Elements Sample element content (wt%) Li 0.7776 S 3.5386

[0110] Table 3

[0111]

[0112]

[0113] Table 4

[0114]

[0115] In summary, the preparation method provided by the present invention uses a drying method and a gas chromatograph to perform qualitative and quantitative analysis on the specific composition of low-boiling-point substances; then, a pyrolysis gas chromatography-mass spectrometer can be used to perform qualitative and quantitative analysis on high-boiling-point substances in the photocurable electrolyte. Based on the pyrolysis gas chromatography-mass spectrometry results, an X-ray fluorescence spectrometer and an inductively coupled plasma emission spectrometer are used to perform elemental analysis on the polymer electrolyte. Then, combined with a nuclear magnetic resonance spectrometer, the lithium salt in the polymer electrolyte is further qualitatively analyzed. The analysis method can quickly, efficiently and accurately obtain the components of an unknown polymer electrolyte, which is of great significance for the recovery, production and research and development of polymer electrolytes.

[0116] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for analyzing the composition of a photocurable polymer electrolyte, characterized in that: The analytical method comprises the following steps: (1) Quantitative analysis of low-boiling-point substances in the photocurable polymer electrolyte by a drying method; qualitative and quantitative analysis of low-boiling-point substances in the photocurable polymer electrolyte by gas chromatography-mass spectrometry; (2) Qualitative and quantitative analysis of polymers in photocurable polymer electrolytes using pyrolysis gas chromatography-mass spectrometry; (3) Qualitative and quantitative analysis of elements in photocurable polymer electrolytes using X-ray fluorescence spectrometer and inductively coupled plasma optical emission spectrometer; (4) Using nuclear magnetic resonance spectroscopy to qualitatively analyze the salt in the photocurable polymer electrolyte; (5) Combining the test results of steps (1) to (4), the composition formula of the photocurable polymer electrolyte is obtained.

2. The analysis method according to claim 1, characterized in that The drying method in step (1) comprises: weighing the photocurable polymer electrolyte to obtain the mass of the photocurable polymer electrolyte before drying; then drying the photocurable polymer electrolyte at 100-200° C. for 4-8 hours, weighing the photocurable polymer electrolyte to obtain the mass of the photocurable polymer electrolyte after drying, thereby obtaining the content of low-boiling-point substances and high-boiling-point substances in the photocurable polymer electrolyte.

3. The analysis method according to claim 1 or 2, characterized in that The test conditions of the gas chromatography-mass spectrometer in step (1) are as follows: Inlet temperature: 280-300°C; carrier gas: helium; flow rate: 0.5-1.5 mL / min; Injection mode: split injection, split ratio 20-50:1; Injection concentration: 0.05-0.2 g / mL; Heating program: Heating program A or Heating program B; The heating program A comprises: maintaining at 30-50°C for 1-5 minutes, heating to 120-160°C at a heating rate of 6-14°C / min, and then heating to 280-310°C at a heating rate of 12-26°C / min; The heating program B includes: maintaining at 30-50°C for 1-5 minutes, heating to 100-140°C at a heating rate of 2-8°C / min, heating to 180-240°C at a heating rate of 10-15°C / min, and then heating to 280-310°C at a heating rate of 20-25°C / min; Ion source temperature: 220-240°C; Interface temperature: 290~310℃; Ionization mode: electron bombardment 70eV; Collection time: 1 to 28 minutes; Scan range: 29-600 m / z.

4. The analysis method according to any one of claims 1 to 3, characterized in that The test conditions of the pyrolysis gas chromatography mass spectrometer in step (2) are as follows: Cracking temperature: 400-800°C, cracking time: 0.1-0.3 min; Inlet temperature: 200-300°C; carrier gas: helium; Flow rate: 0.5-1.5 mL / min; Injection mode: split injection, split ratio 20-50:1; Heating program: Heating program C or heating program D; The heating program C includes: maintaining at 30-50°C for 2-4 minutes, heating to 120-160°C at a heating rate of 6-14°C / min, and then heating to 280-310°C at a heating rate of 15-25°C / min; The heating program D includes: maintaining at 30-50°C for 1-5 minutes, heating to 80-110°C at a heating rate of 1-5°C / min, heating to 140-170°C at a heating rate of 10-15°C / min, and then heating to 280-310°C at a heating rate of 20-25°C / min; Ion source temperature: 210-250°C; Interface temperature: 290~310℃; Ionization mode: electron bombardment 70eV; Collection time: 1 to 28 minutes; Scan range: 29-600 m / z.

5. The analysis method according to any one of claims 1 to 4, characterized in that The test conditions of the X-ray fluorescence spectrometer in step (3) are as follows: Target material: Power ≤ 4kW; including at least one of rhodium target, cobalt target or chromium target; Atmosphere: vacuum; Tube voltage: 20~40kV; Tube current: 50~150mA; Spectral crystal: RX26; Scanning range: 72.02°~78.02°, scanning step: 0.01~0.08°, scanning speed: 2~20° / min.

6. The analysis method according to claim 5, characterized in that The scanning step length of the X-ray fluorescence spectrometer is 0.04-0.06°, and the scanning speed is 5-15° / min.

7. The analysis method according to any one of claims 1 to 6, characterized in that The test conditions of the inductively coupled plasma emission spectrometer in step (3) are as follows: Plasma RF power: 1000~1500W; Working gas: argon, the purity of the argon is ≥99.999%; Plasma gas flow rate: 8-15L / min; Auxiliary gas flow rate: 0.9~1.1L / min; Nebulizer gas flow rate: 0.6~0.8L / min; The peristaltic pump speed is 10-15 rpm.

8. The analysis method according to claim 7, characterized in that The plasma radio frequency power of the inductively coupled plasma emission spectrometer is 1200-1400W; Preferably, the nebulizer gas flow rate of the inductively coupled plasma optical emission spectrometer is 0.68 to 0.75 L / min.

9. The analysis method according to any one of claims 1 to 7, characterized in that The test conditions of the nuclear magnetic resonance spectrometer in step (4) are as follows: Pulse sequence: zg pulse sequence; Spectral width: 200~300HZ; Center point -20~-50ppm; Resonance frequency: 376.48HZ; Sampling times: 16 to 32 times; Acquisition time: 2 to 10 seconds; Relaxation time: 10~20s.

10. Use of the analysis method according to any one of claims 1 to 9 in polymer electrolyte production, polymer electrolyte recovery, and polymer electrolyte research and development.

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