A fully solid-state lithium-ion in-situ testing device

Abstract

The present invention provides an all-solid-state lithium ion in-situ testing device, which comprises a sample device, a charging and discharging system electrically connected to the sample device, and a temperature control system and a detector device respectively arranged on the outside of the sample device; the sample device comprises a connecting component, a sample rod and a battery component, and the battery component is connected to the connecting component through the sample rod; the battery component comprises a top shell, a connecting rod, a battery body and a bottom shell, and the bottom shell is pressed to the lower part of the battery body through a lower pressing nut; the all-solid-state lithium ion in-situ testing device of the present invention can realize an in-situ neutron diffraction experiment on an all-solid-state lithium ion battery under the conditions of applying a temperature field, an electrochemical field and a vacuum environment, and has the advantages of locating the sample position, conveniently replacing positive and negative electrode sheets, and adapting to samples of different sizes.

Description

Technical Field

[0001] The invention relates to the technical field of battery testing, and in particular to an all-solid-state lithium ion in-situ testing device suitable for neutron diffraction experiments. Background Art

[0002] In recent years, with the rapid development of advanced communication terminals, electric vehicles, large-scale energy storage and other fields, the demand for high energy density secondary batteries is urgent. Among various commercial rechargeable and dischargeable chemical energy storage devices, lithium-ion batteries have the highest energy density.

[0003] Solid-state battery technology is one of the solutions that can achieve both high energy density and high safety. All-solid-state lithium batteries use solid electrolytes that do not contain organic solvents. They are non-volatile, non-flammable, stable under high temperature and air conditions, have a wide electrochemical window, have high mechanical strength, and prevent short circuits caused by lithium dendrites, which can greatly improve safety. On the other hand, solid-state batteries can use metallic lithium as the negative electrode material, which greatly improves the energy density of the battery.

[0004] Neutron experimental technology has unique and irreplaceable advantages in the research of the above-mentioned key scientific issues. The interaction between neutrons and matter is different from that between electrons and X-rays. The interaction between neutrons and atomic nuclei is a short-range interaction, and its scattering length does not have an obvious change pattern with the atomic number. Therefore, compared with other methods, neutron scattering is more sensitive and accurate in detecting light elements (such as hydrogen, lithium, oxygen, etc.). In addition, the seeds have good penetrability and are very suitable for non-destructive real-time in-situ characterization of the battery's service and working status. Therefore, neutron technology has irreplaceable unique advantages in the research of solid-state lithium battery materials and devices.

[0005] The Spallation Neutron Source is a large-scale research platform for neutron scattering research and application. It provides an advanced research platform for cutting-edge research in many fields such as materials science and technology, physics, chemistry and chemical engineering, resources and environment, new energy, life sciences, medicine, nanoscience, and for solving key problems that meet many of the country's major strategic needs.

[0006] Neutron scattering spectrometer is a device suitable for neutron scattering experiments, mainly studying the microstructure and movement of matter. This invention is mainly used for experiments on general powder diffraction spectrometers and small-angle scattering spectrometers.

[0007] The general powder diffractometer (GPPD) is an elastic scattering spectrometer, which is mainly used to study the crystal structure and magnetic structure of materials. GPPD uses the neutron time-of-flight technology, selects the appropriate distance from the moderator to the sample (30m), and has three sets of detectors at different angles. The low-angle detector (30°) is suitable for determining the structure of larger crystals; the high-angle backscattering detector (150°) is suitable for research with higher resolution, with a resolution of up to 0.2%; the medium-angle detector (90°) can effectively avoid scattering in the sample cavity. It is suitable for structural research under special sample environments.

[0008] The CSNS small angle scattering instrument is a general-purpose time-of-flight small angle scattering instrument. It uses a 1~12Å pulsed neutron beam from a coupled liquid hydrogen moderator to measure the sample I(q)-q scattering intensity curve and obtains nanoscale inhomogeneous structure information in the sample through model fitting. The CSNS small angle scattering spectrometer adopts the classic point-focusing pinhole camera geometry, and the collimator and neutron aperture limit the beam to achieve collimation and focusing of the neutron beam. The spectrometer adopts a short straight beam line design with a total length of 16 meters. The distance from the sample to the moderator surface is 12 meters, and the distance to the detector (movable) can be adjusted within the range of 2~4 meters. The measured Q range is 0.01-1Å, which can be used to detect the microscopic and mesoscopic structure of the material system within the scale of 1~100nm. Compared with synchrotron radiation, it has a unique contrast transformation technology. Isotope substitution (such as deuteration) can be used to achieve "marking" and selective observation of certain special areas or fragments in the material structure.

[0009] At present, there are few in-situ devices on the market for neutron diffraction experiments on all-solid-state lithium-ion batteries, and the only devices do not cover the experimental conditions required for all-solid-state lithium-ion batteries. For example, the patent "A battery in-situ test device" (application publication number: CN213658936U), although the patent has both a temperature control system and a charging and discharging system, lacks the necessary vacuum environment, and cannot match the connection components in the sample environment of a general powder spectrometer and a small-angle scattering spectrometer, and replacement is cumbersome. In addition, the wide range of applications leads to no relevant optimization for neutron diffraction experiments, and the materials selected for some components will have an adverse effect on the neutron diffraction experiment.

[0010] There is an urgent need to design a special in-situ testing device that can be used for neutron diffraction experiments on all-solid-state lithium-ion batteries, with simple sample replacement, a temperature control system, a charging and discharging system, and a vacuum environment, and a pre-stressing effect on the positive and negative poles of the battery, and can adapt to different sample sizes. Summary of the invention

[0011] The present invention provides a special in-situ testing device for neutron diffraction experiments of all-solid-state lithium-ion batteries, which has a temperature control system, a charging and discharging system and a vacuum environment, and has the advantages of simple sample replacement, the ability to apply pre-pressure to samples, and the ability to eliminate the influence of some materials in the device on the signal of electrode materials.

[0012] One aspect of the present invention provides an all-solid-state lithium ion in-situ testing device, which includes a sample device, a charge and discharge system electrically connected to the sample device, and a temperature control system and a detector device respectively arranged outside the sample device.

[0013] Furthermore, the sample device includes a connecting component, a sample rod and a battery component, and the battery component is connected to the connecting component through the sample rod.

[0014] Furthermore, the battery assembly includes a top shell, a connecting rod, a battery body and a bottom shell, the bottom shell is pressed against the lower part of the battery body by a lower clamping nut; a through hole is provided at the top of the top shell for the connecting rod to extend outward from the inside of the top shell, and the inner diameter of the through hole is equal to the outer diameter of the connecting rod; one end of the connecting rod is connected to the sample rod, and the other end is pressed against the upper part of the battery body by an upper clamping nut; the battery body is arranged between the top shell and the bottom shell.

[0015] Furthermore, the battery body includes an outer shell, a top gasket, a bottom gasket, an insulating sleeve, a positive electrode sheet, a negative electrode sheet and glass fiber; one end of the outer shell is pressed against the lower end of the connecting rod through an upper clamping nut, and the other end is pressed against the bottom shell through a lower clamping nut; the top gasket and the bottom gasket are detachably installed in the outer shell and are arranged between the upper clamping nut and the lower clamping nut; the positive electrode sheet, the negative electrode sheet and the glass fiber are arranged between the top gasket and the bottom gasket, and the glass fiber is coated on the outside of the positive electrode sheet and the negative electrode sheet.

[0016] Furthermore, at least one sealing ring is respectively arranged between the top gasket and the bottom gasket and the outer shell.

[0017] Furthermore, an insulating sleeve is provided between the bottom gasket and the outer shell.

[0018] Furthermore, the connecting assembly includes a circular connecting flange and a mounting flange for mounting the sample rod. The mounting flange is provided with a guide portion for facilitating the installation of the sample rod, and the mounting flange is installed at the center of the circular ring of the connecting flange.

[0019] Furthermore, the temperature control system includes a heating rod arranged on the top gasket, a thermistor arranged on the bottom gasket, and a temperature controller electrically connected to the heating rod and the thermistor respectively.

[0020] Furthermore, the thermistor is a platinum thermistor.

[0021] Furthermore, the temperature range of the temperature control system is 20°C to 100°C.

[0022] Furthermore, the charging and discharging system includes a battery testing system electrically connected to the positive electrode sheet and the negative electrode sheet respectively, and a PC terminal electrically connected to the battery testing system.

[0023] Another aspect of the present invention provides an all-solid-state lithium ion in-situ testing device, which is detachably mounted on a six-dimensional adjustment table of a spectrometer sample.

[0024] Furthermore, the test device is detachably mounted on the six-dimensional adjustment table of the spectrometer sample environment through the sample device.

[0025] Furthermore, the sample device is detachably mounted on the six-dimensional adjustment platform of the spectrometer sample through a connecting component.

[0026] Furthermore, the connection assembly is detachably mounted on the six-dimensional adjustment platform of the spectrometer sample via a connection flange.

[0027] Compared with the prior art, the all-solid-state lithium ion in-situ testing device of the present invention has the following beneficial effects:

[0028] 1. The material of the components in contact with the positive and negative electrodes in the temperature control system is titanium-zirconium alloy, because titanium-zirconium alloy has no diffraction peaks for neutron diffraction. At the same time, the insulation treatment of the positive and negative electrodes and the titanium-zirconium alloy battery shell is glass fiber, which will produce a tiny messy neutron diffraction background after neutron diffraction, which has almost no effect on the regular neutron diffraction signals of the positive and negative electrodes. This is very important for obtaining the neutron diffraction peaks of the positive and negative electrodes, and will not affect their signals. In addition, although the components that are not in direct contact have influencing materials, they are covered with a shielding device-boron nitride on the periphery, so that the neutrons incident in this direction will be absorbed by the boron nitride and will not generate diffraction signals on the relevant materials;

[0029] 2. The connection device used is suitable for the general powder diffraction spectrometer and small-angle diffraction spectrometer of the China Spallation Neutron Source, and is also suitable for other spectrometers, avoiding the need for experimenters to repeatedly design matching connection devices;

[0030] 3. When replacing the sample, there is no need to completely remove the battery body. You only need to remove the bottom PEEK compression nut, bottom titanium-zirconium alloy gasket, PEEK insulation sleeve and large O-ring. No other cumbersome operations are required.

[0031] 4. When calibrating the position of the experimental sample, the time for the sample to be aligned with the neutron beam is reduced, because before the experiment begins, the positions of the positive and negative electrodes are calibrated in advance, and lines are drawn on the outside of the battery body to facilitate alignment when adjusting the spectrometer sample environment displacement stage. At the same time, in order to replace the positive or negative electrode without changing the sample position, a small O-ring is installed at the bottom of the top titanium-zirconium alloy, and the insulation between the top titanium-zirconium alloy and the battery shell is in the form of Capton tape to prevent the position of the positive or negative electrode from changing;

[0032] 5 The all-solid-state lithium ion in-situ test device used in the present invention has fewer parts and is easy to produce and process. The battery device assembly adopts a threaded and hanging method, which is easy to operate and is conducive to the use in actual life and production. In addition, in order to keep the pressing mechanism in close contact with the current collector surface during the battery charging and discharging process, the original spring is changed to a threaded pre-pressing structure, which reduces the number of parts of the battery device and makes the overall device more compact.

[0033] 6. The all-solid-state lithium ion in-situ testing device of the present invention is sealed with an O-ring, with two small O-rings on the upper part and one large O-ring on the lower part. At the same time, the charging and discharging of the positive and negative electrodes and the heating leads are transferred from the electrode itself to the titanium-zirconium alloy gasket in contact with it, eliminating the influence of pores on the sealing performance;

[0034] 7. The all-solid-state lithium ion in-situ testing device of the present invention matches a controllable temperature environment and an in-situ charging and discharging device, and the temperature range is 20-100°C, which meets the testing environment of most batteries;

[0035] 8. The operation of replacing the positive electrode sheet / negative electrode sheet and the positive electrode sheet / negative electrode sheet can be realized by matching titanium-zirconium alloy gaskets of different thicknesses. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is a schematic diagram of the principle structure of the all-solid-state lithium-ion in-situ testing device when in use;

[0037] Figure 2 It is a schematic diagram of the structure of the all-solid-state lithium-ion in-situ testing device;

[0038] Figure 3 is an isometric schematic diagram of a connection device in an all-solid-state lithium-ion in-situ test device;

[0039] Figure 4 is a schematic cross-sectional view of a battery body in an all-solid-state lithium-ion in-situ testing device;

[0040] Figure 5 It is a schematic diagram of the positions of the heating rod and the negative electrode wiring slot in the all-solid-state lithium-ion in-situ test device;

[0041] Figure 6 It is a schematic diagram of the location of thermistors and positive electrode wiring slots in the all-solid-state lithium-ion in-situ test device. DETAILED DESCRIPTION

[0042] The all-solid-state lithium ion in-situ testing device of the present invention will be further described in detail below in conjunction with specific embodiments and drawings. Example

[0043] Reference Figure 1 A non-limiting embodiment of the present invention is an all-solid-state lithium ion in-situ testing device, which is detachably mounted on a six-dimensional adjustment table of a spectrometer sample for neutron diffraction analysis and is a dedicated experimental device for neutron diffraction experiments.

[0044] Reference Figure 1 A non-limiting embodiment of the present invention, an all-solid-state lithium ion in-situ testing device specifically includes a sample device 1, a detector device 2, a temperature control system 3, a charge and discharge system 6 and a light source 5. The sample device 1 is detachably mounted on a six-dimensional adjustment table of a spectrometer sample environment, the temperature control system 3 is disposed on the outside of the sample device 1, the charge and discharge system 6 is electrically connected to the sample device 1, the detector device 2 is disposed on the outside of the sample device 1, and the light source 5 is used to generate a neutron beam.

[0045] Reference Figure 2 In a non-limiting embodiment of the present invention, the sample device 1 includes a connection component 7, a sample rod 15 and a battery component 8. The connection component 7 is detachably mounted on the six-dimensional adjustment table of the spectrometer sample, and the battery component 8 is connected to the connection component 7 through the sample rod 15;

[0046] In addition, the length of the sample rod 15 depends on the height between the six-dimensional adjustment stage of the spectrometer sample environment and the central beam line of the spectrometer.

[0047] Reference Figure 3 In a non-limiting embodiment of the present invention, the connection component 7 includes a circular connection flange 9 and a mounting flange 10 for mounting a sample rod. The connection component 7 is detachably mounted on the six-dimensional adjustment table of the spectrometer sample through the connection flange 9. The mounting flange 10 is mounted at the center of the circular ring of the connection flange 9, and the outer diameter of the mounting flange 10 is equal to the inner diameter of the connection flange 9 to improve the sealing performance; then, a guide portion 14 is provided on the mounting flange 10 to facilitate the installation of the sample rod 15, and at least two small eye screws 11 and a guide pin 12 are respectively provided on the upper surface of the mounting flange 10 for fixing the sample rod on the mounting flange 10, and at least two large eye screws 13 are provided on the upper surface of the connecting flange 9 for moving the connecting flange 9.

[0048] Reference Figure 4In a non-limiting embodiment of the present invention, the battery assembly 8 includes a top shell 19, a connecting rod 21, a battery body and a bottom shell 17. A through hole is provided at the top of the top shell 19 for the connecting rod 21 to extend outward from the inside of the top shell 19. The inner diameter of the through hole is equal to the outer diameter of the connecting rod 21, and the end of the connecting rod 21 is an open groove, whose outer diameter is less than or equal to the inner diameter of the top shell 19, so that the top shell 19 is hung above the end of the connecting rod 21 to improve the sealing of the battery assembly 8. One end of the connecting rod 21 is connected to the sample rod 15, and the other end is pressed against the upper part of the battery body by the upper pressing nut 20. The bottom shell 17 is pressed against the lower part of the battery body by the lower pressing nut 16. At the same time, the battery body is arranged between the top shell 19 and the bottom shell 17; then, the battery body includes an outer shell 18, a top shell 19, and a bottom shell 17. The outer shell 18 comprises a top gasket 22, a bottom gasket 29, an insulating sleeve 28, a positive electrode sheet 25, a negative electrode sheet 24 and a glass fiber 26. One end of the outer shell 18 is pressed against the lower end of the connecting rod 21 by the upper clamping nut 20, and the other end is pressed on the bottom shell 17 by the lower clamping nut 16. Then, the top gasket 22 and the bottom gasket 29 are detachably installed in the outer shell 18 and are arranged between the upper clamping nut 20 and the lower clamping nut 16; the positive electrode sheet 25, the negative electrode sheet 24 and the glass fiber 26 are arranged between the top gasket 22 and the bottom gasket 29, and the glass fiber 26 is coated on the outside of the positive electrode sheet 25 and the negative electrode sheet 24; more specifically, the top gasket 22, the negative electrode sheet 24, the positive electrode sheet 25 and the bottom gasket 29 are arranged from top to bottom in the outer shell 18.

[0049] During the present embodiment, it should be noted that: the top shell 19 and the bottom shell 17 are both made of boron nitride; the connecting rod 21 is made of aluminum; the outer shell 18 of the battery body is a titanium-zirconium alloy battery shell; the upper clamping nut 20 and the lower clamping nut 16 are made of PEEK; the top gasket 22 and the bottom gasket 29 are both titanium-zirconium alloy gaskets.

[0050] Reference Figure 4 In a non-limiting embodiment of the present invention, at least one O-ring is respectively disposed between the top gasket 22 and the bottom gasket 29 and the outer shell 18, and an insulating sleeve 28 is disposed between the bottom gasket 19 and the outer shell 18. For the sake of distinction, at least two O-ring upper seals 23 are disposed between the top gasket 22 and the outer shell 18, and at least one O-ring lower seal 27 is disposed between the bottom gasket 29 and the outer shell 18. Specifically, the insulating sleeve 28 is stepped, and is made of PEEK, and is wrapped around the outer side of the bottom gasket 29, so the lower seal 27 is disposed between the step of the insulating sleeve 28 and the step of the outer shell 18, and a groove for embedding the seal 23 is provided on the side of the top gasket 22, and the glass fiber 26 is coated on the outer side of the negative electrode sheet 24 and the positive electrode sheet 25 to isolate the negative electrode sheet 24 and the positive electrode sheet 25 from contact with the outer shell.

[0051] It can be seen that the top gasket 22, the bottom gasket 29 and the outer shell 18 together constitute a sealed cavity, which is used to provide the sample environment conditions required by the vacuum of the positive electrode 25 and the negative electrode 24, and the connection between the top gasket 22, the bottom gasket 29 and the outer shell 18 is provided with a vacuum seal through the insulating sleeve 28, the upper sealing ring 23 and the lower sealing ring 27.

[0052] Therefore, before the battery assembly 8 is assembled, it is necessary to calibrate the sample. First, determine the position of the lower surface of the top 22, that is, the position of the upper surface of the negative electrode 24, and draw a line at the same position on the outer surface of the outer shell 18. This is the basis for coarse adjustment of the position of the battery assembly 8. Finally, the detector device 2 receives the signal after neutron diffraction from the positive electrode 25 and the negative electrode 24 inside the battery assembly 8, and performs fine adjustment.

[0053] It is easy for those skilled in the art to understand that the top shell (top boron nitride) 19 and the bottom shell (bottom boron nitride) 17 together constitute a shielding body of the battery assembly 8, which is used to shield the neutron diffraction signals generated by other materials except the positive electrode sheet 25 and the negative electrode sheet 24, and avoid the influence on the neutron diffraction background. The materials of the components of the battery assembly 8 close to the positive electrode sheet 25 and the negative electrode sheet 24 are selected from titanium-zirconium alloy except for the glass fiber 26, so that the neutron diffraction peak is almost zero. The glass fiber 26 will produce a tiny and messy neutron diffraction background after neutron diffraction, which has almost no effect on the regular neutron diffraction signals generated by the positive electrode sheet 25 and the negative electrode sheet 24. In addition, although the PEEK insulating sleeve 28, the lower sealing ring 27 and the upper sealing ring 23 have an influence on the neutron diffraction background, they have boron nitride 17 and 19 on the outside, which will absorb neutrons and will not generate neutron signals.

[0054] In addition, Capton tape is also pasted on the top gasket 22 and the outer shell 18 for insulation, and glass fiber 26 is used to realize the insulation between the outer shell 18 and the positive electrode sheet 25 and the negative electrode sheet 24. In addition, PEEK compression nuts 20 and 16 are used to tighten the outer shell at the upper and lower ends. They all have an insulating effect to prevent the experimenter from accidentally touching the outer shell during the test and causing danger.

[0055] Reference Figures 1 to 6 In a non-limiting embodiment of the present invention, the temperature control system 3 includes a temperature controller, a heating rod 30 and a thermistor 33. The heating rod 30 is arranged on the top gasket, and the thermistor 33 is arranged on the bottom gasket. The temperature controller is electrically connected to the heating rod 30 and the thermistor 33 respectively. The temperature controller does not require an additional power supply and can be directly connected to the civil electricity through a plug.

[0056] Reference Figure 5 In a non-limiting embodiment of the present invention, the top gasket 22 is provided with a first groove for mounting the heating rod 30 and a negative electrode connection groove 31 for the lead of the negative electrode sheet 24 .

[0057] Therefore, correspondingly, a lead hole for electrically connecting the lead wires of the heating rod 30 and the negative electrode wiring slot 31 is opened on the link rod 21.

[0058] Reference Figure 6 In a non-limiting embodiment of the present invention, the bottom gasket 29 is provided with a second groove for mounting the thermistor 33 and a positive electrode wiring groove 32 for the lead wire of the positive electrode sheet 25 .

[0059] Reference Figures 1 to 6 In a non-limiting embodiment of the present invention, the heating rod 30 heats the positive electrode sheet 25 and the negative electrode sheet 24 respectively by heat transfer to reach the temperature required for the reaction, and the temperature continues to be transferred, and feedback regulation is achieved through the thermistor 33 to ensure the required sample environment temperature.

[0060] Reference Figures 1 to 6 , the thermistor 33 is a platinum thermal resistor.

[0061] Reference Figures 1 to 6 , the temperature range of the temperature controller is 20℃~100℃.

[0062] Reference Figures 1 to 6 The charging and discharging system 6 includes a battery testing system and a PC terminal 4 electrically connected to the battery testing system. At the same time, the battery testing system is electrically connected to the positive electrode wiring slot 32 and the negative electrode wiring slot 31 respectively to set the charging and discharging conditions and test contents.

[0063] Reference Figure 1 The detector device 2 is used to receive the signal from the light source 5 that is scattered / diffracted by the battery. Example

[0064] Based on solid-state lithium-ion battery testing, the method for using the above-mentioned all-solid-state lithium-ion in-situ testing device mainly includes the following steps:

[0065] S1: In a glove box, assemble the outer shell, top gasket, bottom gasket, positive electrode sheet, negative electrode sheet, glass fiber, insulating sleeve, upper clamping nut, lower clamping nut, upper sealing ring and lower sealing ring into a battery body, and take it out of the glove box;

[0066] S2: Install the heating rod 30 and thermistor 33 of the temperature control system 3 in the top gasket 22 and the bottom gasket 29 respectively, connect the negative electrode wiring slot 32 in the top gasket 22 and the positive electrode wiring slot 31 in the bottom gasket 29 to the charging and discharging system 6 respectively, and connect the connecting rod 21 to the battery assembly 8 through threaded fitting;

[0067] S3: The top boron nitride 19 and the bottom boron nitride 17 are respectively mounted on the lower end of the connecting rod 21 by means of the upper pressing nut 20 and the lower pressing nut 16 to obtain the battery assembly 8;

[0068] S4: The battery assembly 8 is threadedly connected to the lower end of the sample rod 15 through the connecting rod 21, and the upper end of the sample rod 15 is installed on the mounting flange 10 of the connecting assembly 7 through the guide portion;

[0069] S5: The experimenter fixed the entire test device on the six-dimensional adjustment table of the spectrometer sample environment;

[0070] S6: The temperature controller is electrically connected to the heating rod 30 and the thermistor 33 respectively, and then the charge and discharge system 6 is electrically connected to the positive electrode wiring slot 32 and the negative electrode wiring slot 31 respectively, and is connected to the PC terminal 4 outside the scattering chamber of the spectrometer through a data line;

[0071] S7: Start the temperature controller to heat the positive electrode sheet 25 and the negative electrode sheet 24 to reach the ambient temperature required for the experiment, start the charge and discharge system 6, and after confirming that everything is correct, leave the scattering chamber;

[0072] S8: Turn on the neutron beam line switch of the spectrometer to enable the conduction of the neutron beam;

[0073] S9: Start the experiment according to the predetermined experimental plan and save the relevant data.

[0074] Reference Figures 1 to 6 Compared with the prior art, the all-solid-state lithium ion in-situ testing device of the present invention has the following beneficial effects:

[0075] 1. The material of the components in contact with the positive and negative electrodes in the temperature control system is titanium-zirconium alloy, because titanium-zirconium alloy has no diffraction peaks for neutron diffraction. At the same time, the insulation treatment of the positive and negative electrodes and the titanium-zirconium alloy battery shell is glass fiber, which will produce a tiny messy neutron diffraction background after neutron diffraction, which has almost no effect on the regular neutron diffraction signals of the positive and negative electrodes. This is very important for obtaining the neutron diffraction peaks of the positive and negative electrodes, and will not affect their signals. In addition, although the components that are not in direct contact have influencing materials, they are covered with a shielding device-boron nitride on the periphery, so that the neutrons incident in this direction will be absorbed by the boron nitride and will not generate diffraction signals on the relevant materials;

[0076] 2. The connection device used is suitable for the general powder diffraction spectrometer and small-angle diffraction spectrometer of the China Spallation Neutron Source, and is also suitable for other spectrometers, avoiding the need for experimenters to repeatedly design matching connection devices;

[0077] 3. When replacing the sample, there is no need to completely remove the battery body. You only need to remove the bottom PEEK compression nut, bottom titanium-zirconium alloy gasket, PEEK insulation sleeve and large O-ring. No other cumbersome operations are required.

[0078] 4. When calibrating the position of the experimental sample, the time for the sample to be aligned with the neutron beam is reduced, because before the experiment begins, the positions of the positive and negative electrodes are calibrated in advance, and lines are drawn on the outside of the battery body to facilitate alignment when adjusting the spectrometer sample environment displacement stage. At the same time, in order to replace the positive or negative electrode without changing the sample position, a small O-ring is installed at the bottom of the top titanium-zirconium alloy, and the insulation between the top titanium-zirconium alloy and the battery shell is in the form of Capton tape to prevent the position of the positive or negative electrode from changing;

[0079] 5 The all-solid-state lithium ion in-situ test device used in the present invention has fewer parts and is easy to produce and process. The battery device assembly adopts a threaded and hanging method, which is easy to operate and is conducive to the use in actual life and production. In addition, in order to keep the pressing mechanism in close contact with the current collector surface during the battery charging and discharging process, the original spring is changed to a threaded pre-pressing structure, which reduces the number of parts of the battery device and makes the overall device more compact.

[0080] 6. The all-solid-state lithium ion in-situ testing device of the present invention is sealed with an O-ring, with two small O-rings on the upper part and one large O-ring on the lower part. At the same time, the charging and discharging of the positive and negative electrodes and the heating leads are transferred from the electrode itself to the titanium-zirconium alloy gasket in contact with it, eliminating the influence of pores on the sealing performance;

[0081] 7. The all-solid-state lithium ion in-situ testing device of the present invention matches a controllable temperature environment and an in-situ charging and discharging device, and the temperature range is 20-100°C, which meets the testing environment of most batteries;

[0082] 8. The operation of replacing the positive electrode sheet / negative electrode sheet and the positive electrode sheet / negative electrode sheet can be realized by matching titanium-zirconium alloy gaskets of different thicknesses.

[0083] In the description of the present invention, it is necessary to understand that terms such as "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0084] In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0085] The above embodiments are only specific embodiments of the present invention, and their descriptions are relatively specific and detailed, but they cannot be understood as limiting the scope of the present invention. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, and these obvious replacement forms all belong to the protection scope of the present invention.

Claims

1. An all-solid-state lithium ion in-situ testing device, characterized in that: The test device comprises a sample device, a charge and discharge system electrically connected to the sample device, and a temperature control system and a detector device respectively arranged outside the sample device; The sample device comprises a connection assembly, a sample rod and a battery assembly, wherein the battery assembly is connected to the connection assembly through the sample rod, and the battery assembly comprises a top shell, a connecting rod, a battery body and a bottom shell, wherein the bottom shell is pressed against the lower part of the battery body through a lower pressing nut, and a through hole for the connecting rod to extend outward from the top shell is provided on the top of the top shell, wherein the inner diameter of the through hole is equal to the outer diameter of the connecting rod, and one end of the connecting rod is connected to the sample rod, and the other end is pressed against the upper part of the battery body through an upper pressing nut; the battery body is arranged between the top shell and the bottom shell; The battery body includes an outer shell, a top gasket, a bottom gasket, an insulating sleeve, a positive electrode sheet, a negative electrode sheet and glass fiber. One end of the outer shell is pressed against the lower end of the connecting rod by an upper pressing nut, and the other end is pressed on the bottom shell by a lower pressing nut. The top gasket and the bottom gasket are detachably installed in the outer shell and are arranged between the upper pressing nut and the lower pressing nut. The positive electrode sheet, the negative electrode sheet and the glass fiber are arranged between the top gasket and the bottom gasket, and the glass fiber is coated on the outside of the positive electrode sheet and the negative electrode sheet; at least one sealing ring is respectively arranged between the top gasket and the bottom gasket and the outer shell.

2. The all-solid-state lithium ion in-situ testing device according to claim 1, characterized in that: An insulating sleeve is arranged between the bottom gasket and the outer shell.

3. The all-solid-state lithium ion in-situ testing device according to claim 1, characterized in that: The connecting assembly comprises a circular connecting flange and a mounting flange for mounting the sample rod. The mounting flange is provided with a guide portion for facilitating the mounting of the sample rod, and the mounting flange is mounted at the center of the circular ring of the connecting flange.

4. The all-solid-state lithium ion in-situ testing device according to claim 1, characterized in that: The temperature control system comprises a heating rod arranged on the top gasket, a thermistor arranged on the bottom gasket, and a temperature controller electrically connected to the heating rod and the thermistor respectively.

5. The all-solid-state lithium ion in-situ testing device according to claim 4, characterized in that: The thermistor is a platinum thermal resistor.

6. The all-solid-state lithium ion in-situ testing device according to claim 4, characterized in that: The temperature range of the temperature control system is 20°C to 100°C.

7. The all-solid-state lithium ion in-situ testing device according to claim 1, characterized in that: The charging and discharging system includes a battery testing system electrically connected to the positive electrode sheet and the negative electrode sheet respectively, and a PC terminal electrically connected to the battery testing system.

8. An all-solid-state lithium ion in-situ testing device, characterized in that: It comprises the testing device as described in any one of claims 1 to 7, wherein the testing device is detachably mounted on a six-dimensional adjustment table of a spectrometer sample as a whole.

9. The all-solid-state lithium ion in-situ testing device according to claim 8, characterized in that: The testing device is detachably mounted on the six-dimensional adjustment table of the sample environment of the spectrometer through the sample device.

10. The all-solid-state lithium ion in-situ testing device according to claim 9, characterized in that: The sample device is detachably mounted on the spectrometer sample six-dimensional adjustment platform through a connecting component.

11. The all-solid-state lithium ion in-situ testing device according to claim 10, characterized in that: The connecting assembly is detachably mounted on the spectrometer sample six-dimensional adjustment platform via a connecting flange.

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