Bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection equipment and method

Abstract

The present invention discloses a bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device and method, which relates to the field of lithium battery material detection technology, including a sampling device, a precursor derivatization reaction device and a quantitative detection device based on the derivatization component, wherein the sampling device includes multiple sampling ball devices, multiple connecting support devices and a sampling control module, one end of the multiple connecting support devices is respectively installed on the inner wall of the reactor, and the multiple sampling ball devices are respectively installed on the other end of the multiple connecting support devices. The present invention is based on the product in the reaction process undergoing a derivatization reaction to obtain a non-hydrolyzed derivative reactant, and the derivative reactant is subjected to liquid phase quantitative determination, so as to accurately analyze whether the reaction in the preparation process of the bis(fluorosulfonyl)imide lithium salt is complete; specifically, automated control is achieved in sampling, derivatization reaction, solid-liquid separation and powder transportation, so that the detection is automated and the detection error caused by manual use is avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium battery material detection, and in particular to a bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device and method. Background Art

[0002] Lithium battery manufacturing generally consists of five key components: positive electrode, negative electrode, separator, electrolyte, and packaging. Japan was the first to develop and maintain the most mature positive and negative electrode materials. After more than a decade of technological accumulation, China has already surpassed China. Due to Japan's small market and mature gasoline-powered vehicle technology, Japan has little incentive to promote new energy vehicles, making it easy for the country to overtake China.

[0003] The main component of the most widely used electrolyte on the market is lithium hexafluorophosphate. Due to its poor thermal stability, small amounts of water and some anions (such as chloride and sulfate ions) can cause significant damage to the electrolyte. Lithium bis(fluorosulfonyl)imide salts, on the other hand, have high thermal stability and significant advantages over lithium hexafluorophosphate, such as faster charging and no phosphorus pollution. Therefore, replacing lithium hexafluorophosphate is a trend in the current market.

[0004] The current process synthesis of lithium bis(fluorosulfonyl)imide salt is mainly divided into the following three steps:

[0005] 1. In the first step of the reaction, the raw materials sulfamic acid, thionyl chloride and chlorosulfonic acid are subjected to a certain reaction temperature to generate bischlorosulfonyl imide. The raw material thionyl chloride is in excess. The current central control analysis method of the enterprise is to monitor the content of chloride ions, sulfate ions and sulfamic acid phenol ions through ion chromatography. If the sulfamic acid ion content is lower than the enterprise's control index, the reaction is considered to be completed.

[0006] Since both the raw materials and products are hydrolyzed to generate sulfate ions and chloride ions, the results are easily distorted and cannot accurately reflect whether the product has been completely reacted.

[0007] The second step involves the reaction of bischlorosulfonylimide with hydrogen fluoride to produce bisfluorosulfonylimide and hydrogen chloride. The in-process analytical method for this step monitors the fluoride and chloride ion levels. If these levels meet the company's quality standards, the reaction is considered complete. Similarly, because bischlorosulfonylimide readily hydrolyzes, chloride ion detection can distort the accuracy of chloride ion detection. Since fluoride ions are in excess, fluoride ion monitoring carries certain risks and can only partially confirm the completion of the reaction. If the bischlorosulfonylimide ion can be proven to have fully reacted, the aforementioned issues will not apply.

[0008] 3. In the third step, bis(fluorosulfonyl)imide reacts with lithium carbonate to form lithium bis(fluorosulfonyl)imide salt. The intermediate control reaction in this step is determined by titrating lithium carbonate to determine whether the reaction is complete. At the same time, an ion chromatograph is used to detect the fluoride ion, chloride ion and sulfate ion content to confirm that the sample has not been hydrolyzed. Since carbonate ions interfere with sulfate ion content, the intermediate control result has a large error.

[0009] Based on this, existing technologies use precursor derivatization for more accurate measurement. This method involves derivatizing chlorosulfonyl imide ions with aniline under certain conditions to produce a benzene-containing derivative compound that can be detected using standard liquid chromatography. Simultaneously, by preparing a corresponding standard, the quantification of the bis(chlorosulfonyl) imide ion can be achieved. However, this analytical approach lacks reliable analytical detection equipment. Summary of the Invention

[0010] To solve the above technical problems, the present invention provides a bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device and method. The following technical solutions are adopted:

[0011] Bis(fluorosulfonyl)imide) lithium salt precursor derivatization analysis and detection equipment, including a sampling device, a precursor derivatization reaction device and a quantitative detection device based on the derivatization component, the sampling device includes multiple sampling ball devices, multiple connecting support devices and a sampling control module, one end of the multiple connecting support devices is respectively installed on the inner wall of the reactor, the multiple sampling ball devices are respectively installed at the other end of the multiple connecting support devices and are evenly distributed in the internal space of the reactor, the sampling control module respectively controls the execution actions of the multiple sampling ball devices and respectively controls the switch execution actions of the multiple connecting support devices, the precursor derivatization reaction device The device includes a reaction container, an automatic dosing device and a reaction control module. The inlet of the reaction container is connected to the liquid outlet of the sampling device through a pipeline. The automatic dosing device is arranged on the top of the reaction container and is used to add derivatized reactants. The reaction control module is respectively communicated with the sampling control module and the automatic dosing device, and controls the execution action of the reaction container. The reaction container is used to generate a derivatization reaction and perform solid-liquid separation. The inlet of the quantitative detection device is connected to the solid powder outlet of the reaction container. The content of the solid substance produced by the derivatization reaction of the reaction container is determined based on the liquid phase quantitative method, and the determination result is displayed.

[0012] By adopting the above technical solution, the detection principle is based on the fact that chlorosulfonic acid can react with aniline to generate N-phenylaminosulfonic acid, which reacts with sodium hydroxide to generate N-phenylaminosulfonic acid, which is a colorless crystalline powder;

[0013] Bischlorosulfonyl imide reacts with aniline to form bisaniline sulfonyl imide, also a colorless crystalline powder. Because N-phenylsulfamic acid and bisaniline sulfonyl imide derivatives are stable and insoluble in water, liquid phase quantification of bisaniline sulfonyl imide can be used to determine whether the reaction between sulfamic acid, thionyl chloride, and chlorosulfonic acid at a certain reaction temperature to form bischlorosulfonyl imide is complete. Quantifying N-phenylsulfamic acid can also determine the extent of the chlorosulfonic acid reaction. This method fundamentally solves the problem of monitoring reaction completion discussed in the background art.

[0014] In the specific implementation, the sampling device is designed to be implemented by using a sampling ball device. Multiple sampling ball devices are evenly distributed inside the reactor, which can achieve more uniform sampling and avoid the traditional sampling method of only taking the reaction solution in one area, resulting in the measurement results not reflecting the true reaction results.

[0015] The design of the precursor derivatization reaction device can use an automatic dosing device to realize automatic dosing action. The reaction vessel can be used for both derivatization reaction and solid-liquid separation, truly realizing fully automatic sampling. Finally, the solid crystalline powder separated from the reaction vessel is added to the quantitative detection device. The quantitative detection device determines the content based on the liquid phase quantitative method and can display the measurement results. The staff can judge whether the reaction of the lithium salt of bis(fluorosulfonyl)imide is complete based on the measurement results, and thus make targeted process adjustments.

[0016] Optionally, the sampling ball device includes an outer shell, an inner shell, multiple one-way solenoid valves and an outlet solenoid valve. The bottom of the outer shell is arranged at the end of the connecting support device, and multiple collection holes are evenly arranged on the surface. The inner shell is arranged inside the outer shell, and multiple liquid inlet holes corresponding to the positions of the multiple collection holes are evenly arranged on the surface. The multiple liquid inlet holes are connected to the multiple collection holes through collection tubes, and the inner shell is fixed. Multiple one-way solenoid valves are respectively arranged in the collection tubes, and the sampling control modules are respectively controlled and connected to the multiple one-way solenoid valves to realize the control of the liquid flow direction in the collection tube. A collection port is set at the bottom of the inner shell, and the collection port is connected to the top inlet of the connecting support device.

[0017] By adopting the above technical solution, the specific structure of the sampling ball device adopts a double-layer stainless steel ball structure. The outer wall of the outer shell is directly located inside the reactor and is directly in contact with the reaction solution. When sampling is required, multiple one-way solenoid valves and outlet solenoid valves are opened at the same time, and the reaction solution in the reactor flows from multiple collection holes to multiple liquid inlet holes, and then flows into the connecting support device from the collection port at the bottom of the inner shell. A pump can also be set in the connecting support device to provide suction power, making sampling more intelligent and controllable.

[0018] Optionally, the connecting support device includes a support tube, a confluence one-way solenoid valve, a confluence pipe, a sampling main solenoid valve and a sampling pump, one end of the support tube is arranged on the inner wall of the reactor, the bottom of the outer shell of the sampling ball device is arranged at the other end of the support tube, and the confluence port at the bottom of the inner shell is connected to the interior of the support tube, the confluence one-way solenoid valve is arranged at the internal channel of the support tube, the confluence pipe is provided with multiple branch pipes, the branch pipes are connected to one side of the support tube and are connected to the interior of the support tube, one end of the confluence pipe is closed, and the other end is connected to the sampling port arranged on the side of the reactor, the sampling main solenoid valve is arranged in the internal channel of the confluence pipe, the inlet of the sampling pump extracts the liquid to be tested collected in the confluence pipe through the sampling port, and transports it to the inlet of the reaction container, and the sampling control module is respectively controlled and connected to the confluence one-way solenoid valves, the sampling main solenoid valve and the sampling pump of the multiple connecting support devices.

[0019] By adopting the above technical solution, the role of the connecting support device is mainly to support the sampling ball device inside the reactor and to transport the liquid sampled by the sampling ball device to the reaction container. Its structure is mainly a support tube, a confluence tube and a sampling pump, and then combined with the switch control of the confluence one-way solenoid valve and the sampling main solenoid valve to realize the confluence and transportation of the sampled liquid.

[0020] Optionally, the reaction vessel includes a reaction shell, a reaction chamber, a crystal separation device and a crystal conveying device, a dosing port is provided on the top of the reaction shell, and a crystal outlet is provided at the bottom, the reaction chamber is provided inside the reaction shell and is located directly below the dosing port, a solid-liquid mixing outlet is provided at the bottom of the reaction chamber, and a discharge solenoid valve is provided at the liquid-solid-liquid mixing outlet, the crystal separation device includes two stirring devices, a separation chamber, a solid-liquid separation solenoid valve and a solid-liquid separator, the two stirring devices are respectively provided at the bottom of the reaction chamber and are located on both sides of the crystal outlet, for stirring the liquid after the reaction to prevent the crystals from sinking to the bottom, the separation chamber is located below the crystal outlet and is connected to the crystal outlet through the solid-liquid separation solenoid valve and the internal channel, the solid-liquid separation solenoid valve is provided at the bottom of the separation chamber, for filtering out the liquid and retaining the solid crystals on the bottom surface of the separation chamber, the inlet of the crystal conveying device is connected to the outlet opened on the side of the separation chamber, for conveying the solid crystal powder in the separation chamber to the detection inlet of the quantitative detection device, and the reaction control module is respectively connected to each electrical control of the crystal separation device and the crystal conveying device.

[0021] By adopting the above technical solution, the reaction container has two functions: first, to carry out the derivatization reaction; second, to separate the solid crystals after the derivatization reaction and transport them to the detection inlet of the quantitative detection device;

[0022] The reaction chamber cooperates with the automatic dosing device to realize the automatic derivatization reaction. When the derivatization reaction is completed, the crystal separation device can be turned on. Before turning on the crystal separation device, it is necessary to turn on the two stirring devices, stir the solid-liquid mixture evenly, and then open the discharge solenoid valve to prevent the crystals from sinking to the bottom and failing to fully enter the separation chamber. The solid-liquid mixture flows into the separation chamber from the solid-liquid mixing outlet. After completion, the discharge solenoid valve is closed, the solid-liquid separation solenoid valve and the solid-liquid separator are opened, and the liquid is filtered out by the solid-liquid separator and then enters the residual liquid collection device, leaving solid crystals. The crystal conveying device is turned on to convey the solid crystals to the detection inlet of the quantitative detection device.

[0023] The entire process is completed automatically, avoiding errors caused by human operation.

[0024] Optionally, the crystal separation device also includes a hot air blower, an air duct and a blowing valve. The hot air blower is arranged on the outer wall of the reaction shell, and the high-pressure air outlet is connected to the air inlet arranged on one side of the inner wall of the reaction chamber through the air duct. The blowing valve is arranged in the air duct, and the reaction control module is respectively controlled and connected to the hot air blower and the blowing valve.

[0025] By adopting the above technical solution, a hot air blower is specifically used to perform hot air drying on the crystals. After hot air drying, the crystals are powdered and blown up.

[0026] Optionally, the crystal conveying device includes a dust sampling suction pump, a suction pipe, an air shutoff, a sedimentation chamber and an outlet valve. The air inlet of the dust sampling suction pump is connected to the outlet opened on the side of the separation chamber through the suction pipe, and the outlet of the suction pipe is connected to the inlet at the top of the sedimentation chamber. The air shutoff is arranged at the inlet of the sedimentation chamber, and the outlet valve is arranged at the funnel-shaped outlet at the bottom of the sedimentation chamber, and is connected to the detection inlet of the quantitative detection device.

[0027] By adopting the above technical solution, since the crystals are powdered after being air-dried, a dust sampling suction pump is used to draw the dust-like crystalline powder into the sedimentation chamber. Under the action of the air lock, the crystalline powder settles and falls into the detection inlet of the quantitative detection device, realizing automatic transportation and greatly improving the detection efficiency.

[0028] Optionally, the crystal separation device further includes an air filter, which is disposed in the air duct and is used to filter impurities in the air entering and exiting the hot air blower.

[0029] By adopting the above technical solution, the air filter prevents impurities in the air on the outer wall from entering the separation chamber and affecting the detection results.

[0030] Optionally, the sampling control module and the reaction control module are control panels based on a PLC programmable controller, and the quantitative detection device is a fully automatic liquid chromatograph.

[0031] By adopting the above technical solution, the fully automatic liquid chromatograph can perform spectral measurement on the dianiline sulfonyl imide crystals obtained after the derivatization reaction and intelligently output the measurement results accurately and efficiently.

[0032] The derivatization analysis and detection method of bis(fluorosulfonyl)imide lithium salt precursor comprises the following steps:

[0033] Step 1: Add sulfamic acid, thionyl chloride and chlorosulfonic acid as raw materials into a reactor to react and generate bischlorosulfonyl imide;

[0034] Step 2: The sampling control module controls the opening of multiple one-way solenoid valves and the outlet solenoid valve of the sampling ball device, and simultaneously controls the opening of the confluence one-way solenoid valve and the sampling main solenoid valve of the communication support device, and starts the sampling pump to pump the liquid to be tested collected in the sampling ball device into the reaction container;

[0035] Step 3: The reaction control module controls the automatic dosing device to add a derivatization reactant, and the liquid to be tested and the derivatization reactant undergo a derivatization reaction to generate dianiline sulfonyl imide;

[0036] Step 4: After the derivatization reaction is completed, the reaction control module controls the stirring device to start, and after running at a speed of 150 r / min for 20 seconds, the discharge solenoid valve is controlled to open, and the solid-liquid mixture containing the dianiline sulfonyl imide crystals enters the separation chamber;

[0037] Step 5: The reaction control module controls the stirring device to stop, closes the discharge solenoid valve, opens the solid-liquid separation solenoid valve and the solid-liquid separator, and the liquid flows out of the solid-liquid separator to the waste liquid collection device. The dianiline sulfonyl imide crystals are retained, and controls the hot air blower and the blowing valve to open to air-dry the dianiline sulfonyl imide crystals;

[0038] Step 6: The reaction control module controls the dust sampling suction pump, the air shutoff, and the outlet valve to open simultaneously, achieving blowing and suction, and sucking the dusted dianiline sulfonyl imide crystals distributed in the separation chamber into the sedimentation chamber, and after sedimentation, the crystals fall into the detection inlet of the quantitative detection device;

[0039] Step 7: The quantitative detection device determines the content of the dianiline sulfonyl imide crystals based on a liquid phase quantitative method and displays the determination result.

[0040] In summary, the present invention includes at least one of the following beneficial technical effects:

[0041] The present invention provides a derivatization analysis and detection device and method for a bisfluorosulfonyl imide lithium salt precursor. A derivatization reaction is performed on the product in the reaction process to obtain a non-hydrolyzed derivatized reactant. The derivatized reactant is subjected to liquid phase quantitative determination, thereby accurately analyzing whether the reaction in the preparation process of the bisfluorosulfonyl imide lithium salt is complete. Specifically, automated control is achieved in sampling, derivatization reaction, solid-liquid separation, and powder transportation, thereby realizing automated detection and avoiding detection errors caused by manual operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is a schematic diagram of the structural principle of the bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection equipment of the present invention;

[0043] Figure 2 This is a schematic structural diagram of the reaction vessel of the bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection equipment of the present invention;

[0044] Figure 3 This is a schematic structural diagram of a sampling ball device for a bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device of the present invention;

[0045] Figure 4 This is a schematic diagram of the connection principle of the electrical components of the bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection equipment of the present invention.

[0046] Explanation of reference numerals: 1. Sampling ball device; 11. Outer shell; 111. Collection hole; 12. Inner shell; 121. Liquid inlet hole; 13. One-way solenoid valve; 14. Outlet solenoid valve; 15. Collection tube; 2. Connecting support device; 21. Support tube; 22. Converging one-way solenoid valve; 23. Converging pipe; 24. Sampling main solenoid valve; 25. Sampling pump; 3. Sampling control module; 4. Reaction container; 41. Reaction shell; 411. Discharging Solenoid valve; 42. Reaction chamber; 43. Stirring device; 44. Separation chamber; 45. Solid-liquid separation solenoid valve; 46. Solid-liquid separator; 47. Hot air blower; 48. Air duct; 49. Blowing valve; 50. Air filter; 51. Dust sampling suction pump; 52. Suction pipe; 53. Air shutoff; 54. Sedimentation chamber; 55. Outlet valve; 5. Automatic dosing device; 6. Reaction control module; 100. Reactor; 101. Quantitative detection device. DETAILED DESCRIPTION

[0047] The present invention will be further described in detail below with reference to the accompanying drawings.

[0048] The embodiments of the present invention disclose a bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device and method.

[0049] Reference Figures 1-4, Example 1, a bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device, including a sampling device, a precursor derivatization reaction device and a quantitative detection device 101 based on the derivatization component, the sampling device includes multiple sampling ball devices 1, multiple connecting support devices 2 and a sampling control module 3, one end of the multiple connecting support devices 2 is respectively installed on the inner wall of the reactor 100, and the multiple sampling ball devices 1 are respectively installed at the other end of the multiple connecting support devices 2 and are evenly distributed in the internal space of the reactor 100, the sampling control module 3 respectively controls the execution actions of the multiple sampling ball devices 1, and respectively controls the switch execution actions of the multiple connecting support devices 2, the precursor The derivatization reaction device includes a reaction container 4, an automatic dosing device 5 and a reaction control module 6. The inlet of the reaction container 4 is connected to the liquid outlet of the sampling device through a pipeline. The automatic dosing device 5 is arranged on the top of the reaction container 4 and is used to add derivatization reactants. The reaction control module 6 is respectively communicated with the sampling control module 3 and the automatic dosing device 5, and controls the execution action of the reaction container 4. The reaction container 4 is used to produce a derivatization reaction and perform solid-liquid separation. The inlet of the quantitative detection device 101 is connected to the solid powder outlet of the reaction container 4. The content of the solid substance produced by the derivatization reaction of the reaction container 4 is determined based on the liquid phase quantitative method, and the measurement results are displayed.

[0050] The detection principle is based on the fact that chlorosulfonic acid can react with aniline to form N-phenylaminosulfonic acid, which reacts with sodium hydroxide to form N-phenylaminosulfonic acid, a colorless crystalline powder;

[0051] Bischlorosulfonyl imide reacts with aniline to form bisaniline sulfonyl imide, also a colorless crystalline powder. Because N-phenylsulfamic acid and bisaniline sulfonyl imide derivatives are stable and insoluble in water, liquid phase quantification of bisaniline sulfonyl imide can be used to determine whether the reaction between sulfamic acid, thionyl chloride, and chlorosulfonic acid at a certain reaction temperature to form bischlorosulfonyl imide is complete. Quantifying N-phenylsulfamic acid can also determine the extent of the chlorosulfonic acid reaction. This method fundamentally solves the problem of monitoring reaction completion discussed in the background art.

[0052] In a specific implementation, a sampling ball device 1 is used in the design of the sampling device. Multiple sampling ball devices 1 are evenly distributed inside the reactor 100, which can achieve more uniform sampling and avoid the traditional sampling method of sampling only one area of ​​the reaction solution, resulting in the measurement results not reflecting the true reaction results.

[0053] The design of the precursor derivatization reaction device can use an automatic dosing device 5 to realize automatic dosing action. The reaction container 4 can be used for both derivatization reaction and solid-liquid separation, truly realizing fully automatic sampling. Finally, the solid crystalline powder separated from the reaction container 4 is added to the quantitative detection device 101. The quantitative detection device 101 determines the content based on the liquid phase quantitative method and can display the measurement results. The staff can judge whether the reaction of the lithium salt of bis(fluorosulfonyl)imide is complete based on the measurement results, and thus make targeted process adjustments.

[0054] In the second embodiment, the sampling ball device 1 includes an outer shell 11, an inner shell 12, a plurality of one-way solenoid valves 13 and an outlet solenoid valve 14. The bottom of the outer shell 11 is set at the end of the connecting support device 2, and a plurality of collection holes 111 are evenly arranged on the surface. The inner shell 12 is set inside the outer shell 11, and a plurality of liquid inlet holes 121 corresponding to the positions of the plurality of collection holes 111 are evenly arranged on the surface. The plurality of liquid inlet holes 121 are connected to the plurality of collection holes 111 through the collection tube 15 respectively, and the inner shell 12 is fixed. The plurality of one-way solenoid valves 13 are respectively arranged in the collection tube 15. The sampling control module 3 is respectively controlled and connected with the plurality of one-way solenoid valves 13 to realize the control of the flow direction of the liquid in the collection tube 15. A collection port is set at the bottom of the inner shell 12, and the collection port is connected to the top inlet of the connecting support device 2.

[0055] The specific structure of the sampling ball device 1 adopts a double-layer stainless steel ball structure. The outer wall of the outer shell 11 is directly located inside the reactor 100 and is in direct contact with the reaction solution. When sampling is required, multiple one-way solenoid valves 13 and outlet solenoid valves 14 are opened at the same time, and the reaction solution in the reactor 100 flows from the multiple collection holes 111 to the multiple liquid inlet holes 121, and then flows into the connecting support device 2 from the collection port at the bottom of the inner shell 12. A pump can also be set in the connecting support device 2 to provide suction power, making sampling more intelligent and controllable.

[0056] In the third embodiment, the connecting support device 2 includes a support tube 21, a one-way electromagnetic valve 22 for confluence, a confluence pipe 23, a main sampling electromagnetic valve 24 and a sampling pump 25. One end of the support tube 21 is arranged on the inner wall of the reactor 100, the bottom of the outer shell 11 of the sampling ball device 1 is arranged at the other end of the support tube 21, and the confluence port at the bottom of the inner shell 12 is connected to the inside of the support tube 21. The one-way electromagnetic valve 22 is arranged at the internal channel of the support tube 21, and the confluence pipe 23 is provided with a plurality of branch pipes, and the branch pipes are connected to the support tube 2 1 is connected to one side and communicated with the interior of the support tube 21. One end of the manifold 23 is closed, and the other end is communicated with the sampling port set on the side of the reactor 100. The main sampling solenoid valve 24 is set in the internal channel of the manifold 23. The inlet of the sampling pump 25 extracts the liquid to be tested collected in the manifold 23 through the sampling port and delivers it to the inlet of the reaction container 4. The sampling control module 3 is respectively controlled and connected with multiple converging one-way solenoid valves 22, the main sampling solenoid valve 24 and the sampling pump 25 connected to the support device 2.

[0057] The main function of the connecting support device 2 is to support the sampling ball device 1 inside the reactor 100 and transport the liquid sampled by the sampling ball device 1 to the reaction container 4. Its structure mainly consists of a support tube 21, a confluence pipe 23 and a sampling pump 25, and then cooperates with the switch control of the confluence one-way solenoid valve 22 and the sampling main solenoid valve 24 to realize the confluence and transportation of the sampled liquid.

[0058] In the fourth embodiment, the reaction vessel 4 includes a reaction shell 41, a reaction chamber 42, a crystal separation device and a crystal conveying device. The top of the reaction shell 41 is provided with a dosing port, and the bottom is provided with a crystal outlet. The reaction chamber 42 is provided inside the reaction shell 41, directly below the dosing port. The bottom of the reaction chamber 42 is provided with a solid-liquid mixing outlet, and a discharge solenoid valve 411 is provided at the liquid-solid-liquid mixing outlet. The crystal separation device includes two stirring devices 43, a separation chamber 44, a solid-liquid separation solenoid valve 45 and a solid-liquid separator 46. The two stirring devices 43 are respectively provided at the bottom of the reaction chamber 42 and located at the crystal outlet. On both sides, it is used to stir the liquid after the reaction to prevent the crystals from sinking to the bottom. The separation chamber 44 is located below the crystal outlet and is connected to the crystal outlet through the solid-liquid separation solenoid valve 45 and the internal channel. The solid-liquid separation solenoid valve 45 is set at the bottom of the separation chamber 44 to filter out the liquid and retain the solid crystals on the bottom surface of the separation chamber 44. The inlet of the crystal conveying device is connected to the outlet opened on the side of the separation chamber 44 to convey the solid crystal powder in the separation chamber 44 to the detection inlet of the quantitative detection device 101. The reaction control module 6 is respectively connected to each electrical control of the crystal separation device and the crystal conveying device.

[0059] The reaction vessel 4 has two functions: first, to carry out the derivatization reaction; second, to separate the solid crystals after the derivatization reaction and transport them to the detection inlet of the quantitative detection device 101;

[0060] The reaction chamber 42 cooperates with the automatic dosing device 5 to realize the automatic derivatization reaction. When the derivatization reaction is completed, the crystal separation device can be turned on. Before turning on the crystal separation device, it is necessary to turn on the two stirring devices 43, stir the solid-liquid mixture evenly, and then open the discharge solenoid valve 411 to prevent the crystals from sinking to the bottom and failing to fully enter the separation chamber 44. The solid-liquid mixture flows into the separation chamber 44 from the solid-liquid mixing outlet. After completion, the discharge solenoid valve 411 is closed, the solid-liquid separation solenoid valve 45 and the solid-liquid separator 46 are opened, and the liquid is filtered out by the solid-liquid separator 46 and then enters the residual liquid collection device. What is left is solid crystals. The crystal conveying device is turned on to convey the solid crystals to the detection inlet of the quantitative detection device 101.

[0061] The entire process is completed automatically, avoiding errors caused by human operation.

[0062] In embodiment five, the crystal separation device also includes a hot air blower 47, an air duct 48 and a blowing valve 49. The hot air blower 47 is arranged on the outer wall of the reaction shell 41, and the high-pressure air outlet is connected to the air inlet arranged on one side of the inner wall of the reaction chamber 42 through the air duct 48. The blowing valve 49 is arranged in the air duct 48, and the reaction control module 6 is respectively controlled and connected with the hot air blower 47 and the blowing valve 49.

[0063] Specifically, a hot air blower 47 is used to dry the crystals. After drying, the crystals are powdered and blown up.

[0064] In the sixth embodiment, the crystal conveying device includes a dust sampling suction pump 51, a suction pipe 52, an air shutoff 53, a sedimentation chamber 54 and an outlet valve 55. The air inlet of the dust sampling suction pump 51 is connected to the outlet opened on the side of the separation chamber 44 through the suction pipe 52. The outlet of the suction pipe 52 is connected to the inlet at the top of the sedimentation chamber 54. The air shutoff 53 is arranged at the inlet of the sedimentation chamber 54. The outlet valve 55 is arranged at the funnel-shaped outlet at the bottom of the sedimentation chamber 54 and is connected to the detection inlet of the quantitative detection device 101.

[0065] Since the crystals are powdered after being air-dried, a dust sampling suction pump 51 is used to draw the dust-like crystal powder into the sedimentation chamber 54. Under the action of the air lock 53, the crystal powder settles and falls into the detection inlet of the quantitative detection device 101, realizing automatic transportation and greatly improving the detection efficiency.

[0066] The crystal separation device further includes an air filter 50 , which is disposed in the air duct 48 and is used to filter impurities in the air entering and exiting the hot air blower 47 .

[0067] The air filter 50 prevents impurities in the air on the outer wall from entering the separation chamber 44 and affecting the detection results.

[0068] The sampling control module 3 and the reaction control module 6 are control panels based on PLC programmable controllers, respectively, and the quantitative detection device 101 is a fully automatic liquid chromatograph.

[0069] The fully automatic liquid chromatograph can perform spectral measurement on the dianiline sulfonyl imide crystals obtained after the derivatization reaction and intelligently output the measurement results accurately and efficiently.

[0070] Example 7, bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection method, the specific steps are:

[0071] Step 1: Add sulfamic acid, thionyl chloride and chlorosulfonic acid as raw materials into the reactor 100 to react and generate bischlorosulfonyl imide;

[0072] Step 2: The sampling control module 3 controls the multiple one-way solenoid valves 13 and the outlet solenoid valve 14 of the sampling ball device 1 to open, and simultaneously controls the confluence one-way solenoid valve 22 and the sampling main solenoid valve 24 of the communication support device 2 to open, and starts the sampling pump 25 to pump the liquid to be tested collected in the sampling ball device 1 into the reaction container 4;

[0073] Step 3: The reaction control module 6 controls the automatic dosing device 5 to add a derivatization reactant, and the liquid to be detected and the derivatization reactant undergo a derivatization reaction to generate dianiline sulfonyl imide;

[0074] Step 4: After the derivatization reaction is completed, the reaction control module 6 controls the stirring device 43 to start, and after operating at a speed of 150 r / min for 20 seconds, the discharge solenoid valve 411 is controlled to open, and the solid-liquid mixture containing the dianiline sulfonyl imide crystals enters the separation chamber 44;

[0075] Step 5: The reaction control module 6 controls the stirring device 43 to stop, closes the discharge solenoid valve 411, opens the solid-liquid separation solenoid valve 45 and the solid-liquid separator 46, and the liquid flows out of the solid-liquid separator 46 to the waste liquid collection device. The dianiline sulfonyl imide crystals are retained. The hot air blower 47 and the air blowing valve 49 are controlled to open to air-dry the dianiline sulfonyl imide crystals.

[0076] Step 6: The reaction control module 6 controls the dust sampling suction pump 51, the air shutoff 53, and the outlet valve 55 to open simultaneously, achieving blowing and suction, and sucking the dusted dianiline sulfonyl imide crystals distributed in the separation chamber 44 into the sedimentation chamber 54. After sedimentation, the crystals fall into the detection inlet of the quantitative detection device 101.

[0077] In step 7, the quantitative detection device 101 determines the content of the dianiline sulfonyl imide crystals based on a liquid phase quantitative method and displays the determination result.

[0078] The above are all preferred embodiments of the present invention, and are not intended to limit the scope of protection of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the scope of protection of the present invention.

Claims

1. Bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection equipment, characterized by: The invention comprises a sampling device, a precursor derivatization reaction device and a quantitative detection device (101) based on a derivatized component, wherein the sampling device comprises a plurality of sampling ball devices (1), a plurality of connecting support devices (2) and a sampling control module (3), wherein one end of the plurality of connecting support devices (2) is respectively mounted on the inner wall of a reactor (100), and the plurality of sampling ball devices (1) are respectively mounted on the other end of the plurality of connecting support devices (2) and are evenly distributed in the inner space of the reactor (100), and the sampling control module (3) respectively controls the execution actions of the plurality of sampling ball devices (1) and the switch execution actions of the plurality of connecting support devices (2). The precursor derivatization reaction device comprises a reaction container (4), An automatic dosing device (5) and a reaction control module (6); the inlet of the reaction container (4) is connected to the liquid outlet of the sampling device through a pipeline; the automatic dosing device (5) is arranged on the top of the reaction container (4) and is used to add a derivatization reactant; the reaction control module (6) is respectively connected to the sampling control module (3) and the automatic dosing device (5) and controls the execution of the reaction container (4); the reaction container (4) is used to generate a derivatization reaction and perform solid-liquid separation; the inlet of the quantitative detection device (101) is connected to the solid powder outlet of the reaction container (4); the content of the solid substance generated by the derivatization reaction of the reaction container (4) is measured based on a liquid phase quantitative method, and the measurement result is displayed; The sampling ball device (1) comprises an outer shell (11), an inner shell (12), a plurality of one-way solenoid valves (13) and an outlet solenoid valve (14); the bottom of the outer shell (11) is arranged at the end of the communication support device (2), and a plurality of collection holes (111) are evenly arranged on the outer surface; the inner shell (12) is arranged inside the outer shell (11), and a plurality of liquid inlet holes (121) corresponding to the positions of the plurality of collection holes (111) are evenly arranged on the outer surface; the plurality of liquid inlet holes (121) are respectively connected to the plurality of collection holes (111) through a collection tube (15), and the inner shell (12) is fixed; the plurality of one-way solenoid valves (13) are respectively arranged in the collection tube (15); the sampling control module (3) is respectively connected to the plurality of one-way solenoid valves (13) to control the flow direction of the liquid in the collection tube (15); a collection port is provided at the bottom of the inner shell (12), and the collection port is connected to the top inlet of the communication support device (2).

2. The bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device according to claim 1, characterized in that: The communication support device (2) comprises a support pipe (21), a confluence one-way electromagnetic valve (22), a confluence pipe (23), a sampling main electromagnetic valve (24) and a sampling pump (25); one end of the support pipe (21) is arranged on the inner wall of the reactor (100); the bottom of the outer shell (11) of the sampling ball device (1) is arranged at the other end of the support pipe (21); and the confluence port at the bottom of the inner shell (12) is communicated with the interior of the support pipe (21); the confluence one-way electromagnetic valve (22) is arranged at the internal channel of the support pipe (21); the confluence pipe (23) is provided with a plurality of branch pipes, and the branch pipes are connected to the support pipe (21). One side of the tube (21) is connected and communicated with the interior of the support tube (21); one end of the manifold (23) is closed, and the other end is communicated with a sampling port provided on the side of the reactor (100); the main sampling solenoid valve (24) is provided in the internal channel of the manifold (23); the inlet of the sampling pump (25) extracts the liquid to be tested collected in the manifold (23) through the sampling port and delivers it to the inlet of the reaction container (4); the sampling control module (3) is respectively controlled and connected with a plurality of manifold one-way solenoid valves (22) connected to the support device (2), the main sampling solenoid valve (24) and the sampling pump (25).

3. The bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device according to claim 2, characterized in that: The reaction container (4) comprises a reaction shell (41), a reaction chamber (42), a crystal separation device and a crystal conveying device. The top of the reaction shell (41) is provided with a drug addition port, and the bottom is provided with a crystal outlet. The reaction chamber (42) is provided inside the reaction shell (41) and is located directly below the drug addition port. The bottom of the reaction chamber (42) is provided with a solid-liquid mixing outlet, and a discharge electromagnetic valve (411) is provided at the liquid-solid-liquid mixing outlet. The crystal separation device comprises two stirring devices (43), a separation chamber (44), a solid-liquid separation electromagnetic valve (45) and a solid-liquid separator (46). The two stirring devices (43) are respectively provided at the bottom of the reaction chamber (42) and are located at the crystal The two sides of the outlet are used to stir the liquid after the reaction to prevent the crystals from sinking to the bottom. The separation chamber (44) is located below the crystal outlet and is connected to the crystal outlet through a solid-liquid separation electromagnetic valve (45) and an internal channel. The solid-liquid separation electromagnetic valve (45) is set at the bottom of the separation chamber (44) and is used to filter out the liquid and retain the solid crystals on the bottom surface of the separation chamber (44). The inlet of the crystal conveying device is connected to the outlet opened on the side of the separation chamber (44) and is used to convey the solid crystal powder in the separation chamber (44) to the detection inlet of the quantitative detection device (101). The reaction control module (6) is respectively connected to the electrical control of each electrical appliance of the crystal separation device and the crystal conveying device.

4. The bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device according to claim 3, characterized in that: The crystal separation device further comprises a hot air blower (47), an air duct (48) and a blowing valve (49); the hot air blower (47) is arranged on the outer wall of the reaction shell (41); the high-pressure air outlet is communicated with the air inlet arranged on one side of the inner wall of the reaction chamber (42) through the air duct (48); the blowing valve (49) is arranged in the air duct (48); and the reaction control module (6) is respectively controlled and connected to the hot air blower (47) and the blowing valve (49).

5. The bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device according to claim 4, characterized in that: The crystal conveying device includes a dust sampling suction pump (51), a suction pipe (52), an air shutoff (53), a sedimentation chamber (54) and an outlet valve (55). The air inlet of the dust sampling suction pump (51) is connected to the outlet opened on the side of the separation chamber (44) through the suction pipe (52), and the outlet of the suction pipe (52) is connected to the inlet at the top of the sedimentation chamber (54). The air shutoff (53) is arranged at the inlet of the sedimentation chamber (54), and the outlet valve (55) is arranged at the funnel-shaped outlet at the bottom of the sedimentation chamber (54) and is connected to the detection inlet of the quantitative detection device (101).

6. The bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device according to claim 4, characterized in that: The crystal separation device further comprises an air filter (50), which is arranged in the air duct (48) and is used to filter impurities in the air entering and exiting the hot air blower (47).

7. The bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device according to claim 5, characterized in that: The sampling control module (3) and the reaction control module (6) are control panels based on PLC programmable controllers, respectively, and the quantitative detection device (101) is a fully automatic liquid chromatograph.

8. A method for analyzing and detecting a precursor of a lithium bis(fluorosulfonyl)imide salt, characterized in that: The bis(fluorosulfonyl)imide lithium salt precursor derivatization analysis and detection device according to claim 7 is used for detection, and the specific steps are: Step 1: Add sulfamic acid, thionyl chloride and chlorosulfonic acid as raw materials into a reactor (100) to react and generate bischlorosulfonyl imide; Step 2: The sampling control module (3) controls the opening of the multiple one-way solenoid valves (13) and the outlet solenoid valve (14) of the sampling ball device (1), and simultaneously controls the opening of the confluence one-way solenoid valve (22) and the sampling main solenoid valve (24) of the communication support device (2), and starts the sampling pump (25) to pump the liquid to be tested collected in the sampling ball device (1) into the reaction container (4); Step 3: The reaction control module (6) controls the automatic dosing device (5) to add a derivatization reactant, and the liquid to be detected and the derivatization reactant undergo a derivatization reaction to generate dianiline sulfonyl imide; Step 4: After the derivatization reaction is completed, the reaction control module (6) controls the stirring device (43) to start, and after working at a speed of 150 r / min for 20 seconds, the discharge solenoid valve (411) is controlled to open, and the solid-liquid mixture containing the dianiline sulfonyl imide crystals enters the separation chamber (44); Step 5: The reaction control module (6) controls the stirring device (43) to stop, closes the discharge solenoid valve (411), opens the solid-liquid separation solenoid valve (45) and the solid-liquid separator (46), and the liquid flows out of the solid-liquid separator (46) to the waste liquid collection device. The dianiline sulfonyl imide crystals are retained, and the hot air blower (47) and the blowing valve (49) are controlled to open to air-dry the dianiline sulfonyl imide crystals. Step 6, the reaction control module (6) controls the dust sampling suction pump (51), the air shutoff (53) and the outlet valve (55) to open simultaneously, so as to realize blowing and suctioning, and the dusted dianiline sulfonyl imide crystals distributed in the separation chamber (44) are sucked into the sedimentation chamber (54), and after sedimentation, fall into the detection inlet of the quantitative detection device (101); Step 7: The quantitative detection device (101) determines the content of the dianiline sulfonyl imide crystals based on a liquid phase quantitative method and displays the determination result.

Images