All-solid-state lithium ion in-situ testing device and use method thereof

Abstract

The present invention relates to the field of battery testing technology, and more specifically to an all-solid-state lithium ion in-situ testing device suitable for neutron diffraction experiments and a method for using the same. The all-solid-state lithium ion in-situ testing device comprises a sample device, a temperature control system, a charge-discharge system, and a detector device. The temperature control system is located at the top and bottom of the sample device, the charge-discharge system is connected to the sample device via leads, and the detector device is located around the sample device. The all-solid-state lithium ion in-situ testing device of the present invention can perform in-situ neutron diffraction experiments on all-solid-state lithium ion batteries under the conditions of an applied temperature field, an electrochemical field, and a vacuum environment. It also has the advantages of locating sample positions, conveniently replacing positive and negative electrodes, and adapting to samples of different sizes.

Description

Technical Field

[0001] The present 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 and a method for using the same. Background Art

[0002] With the rapid development of advanced communications devices, electric vehicles, and large-scale energy storage in recent years, the demand for high-energy-density secondary batteries has become increasingly urgent. Among various commercially available rechargeable and dischargeable chemical energy storage devices, lithium-ion batteries possess the highest energy density, prompting many countries around the world to establish lithium battery development plans and R&D targets.

[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, 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 way neutrons interact with matter is different from that of electrons and X-rays. The interaction between neutrons and atomic nuclei is a short-range interaction, and its scattering length does not show 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 batteries in 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 applications. 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 spectrometers are devices suitable for neutron scattering experiments, mainly studying the microstructure and movement of matter. This invention is mainly used in general powder diffractometers and small-angle scattering spectrometers for experiments.

[0007] The General Powder Diffractometer (GPPD) is an elastic scattering spectrometer primarily used to study the crystal and magnetic structures of materials. The GPPD utilizes neutron time-of-flight technology, selects an appropriate moderator-sample distance (30m), and features three detectors at different angles. The low-angle detector (30°) is suitable for determining the structure of larger crystals; the high-angle backscatter detector (150°) is suitable for higher-resolution studies, achieving resolutions up to 0.2%; and the medium-angle detector (90°) effectively avoids scattering in the sample cavity. It is suitable for structural studies under challenging sample conditions.

[0008] The CSNS small-angle scatterometer is a general-purpose time-of-flight small-angle scatterometer that uses the The pulsed neutron beam is used to measure the I(q)-q scattering intensity curve of the sample, and the nanoscale inhomogeneous structure information in the sample is obtained 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 to 4 meters. The Q range it measures is It can be used to probe the microscopic and mesoscopic structure of material systems within the 1-100nm range. Compared to synchrotron radiation, it offers unique contrast conversion technology. It can "mark" and selectively observe specific regions or fragments within a material structure through isotope substitution (e.g., deuterium substitution).

[0009] Currently, there are few in-situ devices on the market for conducting neutron diffraction experiments on all-solid-state lithium-ion batteries, and the existing devices do not fully cover the experimental conditions required for all-solid-state lithium-ion batteries. For example, the patent "A Battery In-situ Testing Device" (application publication number: CN213658936U) has both a temperature control system and a charging and discharging system, but lacks the necessary vacuum environment. In addition, the connection components cannot be matched under 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 dedicated in-situ testing device for neutron diffraction experiments on all-solid-state lithium-ion batteries, which can easily replace samples, has a temperature control system, a charging and discharging system, and a vacuum environment, and has 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 charge and discharge system, and a vacuum environment. It has the advantages of simple sample replacement, the ability to apply pre-pressure to the sample, and the ability to eliminate the influence of some materials in the device on the signal of the electrode material.

[0012] One 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 platform of a spectrometer sample.

[0013] Another aspect of the present invention provides an all-solid-state lithium ion in-situ testing device, which includes a sample device, a temperature control system, a charge and discharge system, and a detector device;

[0014] The sample device is detachably mounted on the six-dimensional adjustment platform of the spectrometer sample environment;

[0015] The temperature control system is arranged outside the sample device;

[0016] The charging and discharging system is electrically connected to the sample device;

[0017] The detector device is arranged outside the sample device.

[0018] Furthermore, the sample device includes a connection assembly, a sample rod and a battery assembly;

[0019] The connecting component is detachably mounted on the six-dimensional adjustment platform of the spectrometer sample;

[0020] The battery assembly is connected to the connecting assembly via a sample rod.

[0021] Furthermore, the connecting assembly includes an annular connecting flange and a mounting flange for mounting the sample rod;

[0022] The connecting assembly is detachably mounted on the spectrometer sample six-dimensional adjustment platform via a connecting flange;

[0023] The mounting flange is mounted at the center of the circular ring of the connecting flange, and the outer diameter of the mounting flange is equal to the inner diameter of the connecting flange;

[0024] The mounting flange is provided with a guide portion for facilitating the installation of the sample rod.

[0025] Furthermore, the battery assembly includes a top shell, a connecting rod, a battery body and a bottom shell;

[0026] A through hole is provided on the top of the top shell for the link rod to extend outward from the top shell, and the inner diameter of the through hole is equal to the outer diameter of the link rod;

[0027] One end of the link rod is connected to the sample rod, and the other end is pressed against the upper part of the battery body through the upper pressing nut;

[0028] The bottom shell is pressed against the lower part of the battery body by a lower pressing nut;

[0029] The battery body is arranged between the top shell and the bottom shell.

[0030] Furthermore, the battery body includes a shell, a top gasket, a bottom gasket, an insulating sleeve, a positive electrode sheet, a negative electrode sheet and glass fiber;

[0031] One end of the housing is pressed against the lower end of the link rod through an upper pressing nut, and the other end is pressed against the bottom housing through a lower pressing nut;

[0032] The top gasket and the bottom gasket are detachably mounted in the housing and are disposed between the upper compression nut and the lower compression nut;

[0033] 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.

[0034] Furthermore, at least one sealing ring is provided between the top gasket, the bottom gasket and the outer shell respectively.

[0035] Furthermore, an insulating sleeve is provided between the bottom gasket and the outer shell.

[0036] Furthermore, the temperature control system includes a temperature controller, a heating rod and a thermistor;

[0037] The heating rod is arranged on the top gasket;

[0038] The thermistor is arranged on the bottom gasket;

[0039] The temperature controller is electrically connected to the heating rod and the thermistor respectively.

[0040] Furthermore, the thermistor is a platinum thermistor.

[0041] Furthermore, the temperature range of the temperature control system is 20-100°C.

[0042] Furthermore, the charging and discharging system includes a battery testing system and a PC terminal;

[0043] The PC is electrically connected to the battery testing system;

[0044] The battery testing system is electrically connected to the positive electrode sheet and the negative electrode sheet respectively.

[0045] Furthermore, the detector device is used to receive light source signals scattered or diffracted by the battery.

[0046] Another aspect of the present invention provides a method for using an all-solid-state lithium ion in-situ testing device, which mainly includes the following steps:

[0047] S1: Assemble the battery body in the glove box and take it out of the glove box;

[0048] S2: Install the heating rod and thermistor in the top and bottom gaskets of the battery body respectively;

[0049] S3: Next, the top shell and the bottom shell are mounted on the lower end of the connecting rod by means of upper and lower compression nuts to obtain a battery assembly.

[0050] S4: The battery assembly is installed at the lower end of the sample rod. Then, the upper end of the sample rod is installed on the mounting flange of the connection assembly.

[0051] S5: The entire test device is fixedly mounted on the spectrometer sample six-dimensional adjustment table;

[0052] S6: The temperature controller is electrically connected to the heating rod and the thermistor respectively. Then, the charging and discharging system is electrically connected to the wiring slot and connected to the PC outside the spectrometer scattering chamber via a data cable.

[0053] S7: Start the temperature controller to heat the positive and negative electrodes to the required ambient temperature for the experiment, start the charge and discharge test system, and leave the scattering chamber after confirming that everything is correct.

[0054] S8: Turn on the neutron beam line switch of the spectrometer to enable the conduction of the neutron beam;

[0055] S9: Start the experiment according to the predetermined experimental plan and save the relevant data.

[0056] Another aspect of the present invention provides an application of an all-solid-state lithium ion in-situ testing device, which includes neutron diffraction analysis and is an experimental device dedicated to neutron diffraction experiments.

[0057] Compared with the prior art, the all-solid-state lithium ion in-situ testing device of the present invention has the following beneficial effects:

[0058] 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 made of glass fiber, which will produce a tiny and chaotic neutron diffraction background after neutron diffraction, but has almost no effect on the regular neutron diffraction signals produced by the positive and negative electrodes. This is crucial 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. In this way, neutrons incident in this direction will be absorbed by the boron nitride and will not produce diffraction signals on the relevant materials.

[0059] 2. The connection device used is suitable for the general powder diffractometer and small-angle diffractometer of the China Spallation Neutron Source, and is also applicable to other spectrometers, avoiding the need for experimenters to repeatedly design supporting connection devices;

[0060] 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 tedious operations are required.

[0061] 4. When calibrating the position of the experimental sample, the time for aligning the sample 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 not change the sample position when replacing the positive or negative electrode, 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;

[0062] 5. The all-solid-state lithium-ion in-situ testing device used in the present invention has fewer components and is easy to produce and process. The battery device is assembled in a threaded and hanging manner, which is easy to operate and is conducive to its use in actual life and production. In addition, the clamping mechanism that maintains close contact with the current collector surface during battery charging and discharging is changed from the original spring to a threaded pre-compression structure, reducing the number of components of the battery device and making the overall device more compact.

[0063] 6. The all-solid-state lithium ion in-situ testing device of the present invention is sealed with O-rings, 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 electrodes themselves to the titanium-zirconium alloy gasket in contact with them, eliminating the influence of pores on the sealing performance;

[0064] 7. The all-solid-state lithium-ion in-situ testing device of the present invention is matched with a controllable temperature environment and an in-situ charge and discharge device, with a temperature range of 20 to 100°C, which meets the testing environment of most batteries;

[0065] 8. The operation of replacing the positive / negative electrode sheet and the positive / negative electrode sheet can be achieved by matching titanium-zirconium alloy gaskets of different thicknesses. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is a schematic diagram of the principle structure of the all-solid-state lithium-ion in-situ testing device when in use;

[0067] Figure 2 It is a schematic diagram of the structure of the all-solid-state lithium-ion in-situ testing device;

[0068] Figure 3 is an isometric schematic diagram of a connection device in an all-solid-state lithium-ion in-situ testing device;

[0069] Figure 4 is a schematic cross-sectional view of a battery body in an all-solid-state lithium-ion in-situ testing device;

[0070] Figure 5 This is a schematic diagram of the positions of the heating rod and the negative electrode terminal slot in the all-solid-state lithium-ion in-situ test device;

[0071] Figure 6 This is a schematic diagram of the locations of thermistors and positive electrode wiring slots in the all-solid-state lithium-ion in-situ testing device. DETAILED DESCRIPTION

[0072] The all-solid-state lithium ion in-situ testing device of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings.

[0073] Example 1

[0074] 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.

[0075] Reference Figure 1 In 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.

[0076] Reference Figure 2In a non-limiting embodiment of the present invention, the sample device 1 includes a connecting assembly 7, a sample rod 15 and a battery assembly 8. The connecting assembly 7 is detachably mounted on the six-dimensional adjustment table of the spectrometer sample. The battery assembly 8 is connected to the connecting assembly 7 through the sample rod 15.

[0077] 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.

[0078] Reference Figure 3 In a non-limiting embodiment of the present invention, the connecting assembly 7 includes a circular connecting flange 9 and a mounting flange 10 for mounting a sample rod. The connecting assembly 7 is detachably mounted on the six-dimensional adjustment stage of the spectrometer sample through the connecting flange 9. The mounting flange 10 is mounted at the center of the circular ring of the connecting flange 9, and the outer diameter of the mounting flange 10 is equal to the inner diameter of the connecting 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.

[0079] Reference Figure 4 , 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, the top of the top shell 19 is provided with a through hole 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, the outer diameter of which 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, and 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, a connecting rod 21, and a bottom shell 17. The top gasket 22, the bottom gasket 29, the insulating sleeve 28, the positive electrode sheet 25, the negative electrode sheet 24 and the glass fiber 26, one end of the outer shell 18 is pressed against the lower end of the connecting rod 21 through the upper pressing nut 20, and the other end is pressed on the bottom shell 17 through the lower pressing 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 pressing nut 20 and the lower pressing 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.

[0080] During this 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 battery body shell 18 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.

[0081] Reference Figure 4 In a non-limiting embodiment of the present invention, at least one O-ring is respectively provided between the top gasket 22 and the bottom gasket 29 and the outer shell 18, and an insulating sleeve 28 is provided between the bottom gasket 19 and the outer shell 18. For clarity, at least two upper O-rings 23 are provided between the top gasket 22 and the outer shell 18, and at least one lower O-ring 27 is provided between the bottom gasket 29 and the outer shell 18. Specifically, the insulating sleeve 28 is stepped and made of PEEK, and is wrapped around the outside of the bottom gasket 29. Therefore, the lower sealing ring 27 is provided between the step of the insulating sleeve 28 and the step of the outer shell 18. A groove for embedding the sealing ring 23 is provided on the side of the top gasket 22. Glass fiber 26 is wrapped around the outside 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.

[0082] 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.

[0083] 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 shell 18. This is the basis for coarse adjustment of the position of the battery assembly 8. Finally, fine adjustment is performed through the signal received by the detector device 2 after neutron diffraction from the positive electrode 25 and the negative electrode 24 inside the battery assembly 8.

[0084] 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 the shielding body of the battery assembly 8, which is used to shield the neutron diffraction signals generated by materials other than the positive electrode 25 and the negative electrode 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 25 and the negative electrode 24 are selected from titanium-zirconium alloy except for the glass fiber 26, so that the neutron diffraction peak is almost zero. After neutron diffraction, the glass fiber 26 will produce a tiny and messy neutron diffraction background, which has almost no effect on the regular neutron diffraction signals generated by the positive electrode 25 and the negative electrode 24. In addition, although the PEEK insulating sleeve 28, the lower sealing ring 27 and the upper sealing ring 23 have an impact 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.

[0085] 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 insulate the outer shell 18 from the positive electrode 25 and the negative electrode 24. In addition, PEEK compression nuts 20 and 16 are used to tighten the outer shell at the upper and lower ends. They both have an insulating effect to prevent accidental contact by the experimenter during the test, which may cause danger.

[0086] 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.

[0087] 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 .

[0088] Therefore, correspondingly, a lead hole is opened on the link rod 21 for electrically connecting the lead wires of the heating rod 30 and the negative electrode terminal slot 31.

[0089] 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 connection groove 32 for the lead of the positive electrode sheet 25 .

[0090] Reference Figures 1 to 6 In a non-limiting embodiment of the present invention, the heating rod 30 heats the positive electrode 25 and the negative electrode 24 respectively by heat transfer to reach the temperature required for the reaction, and the temperature continues to be transferred, and feedback adjustment is achieved through the thermistor 33 to ensure the sample environment temperature requirements.

[0091] Reference Figures 1 to 6 , the thermistor 33 is a platinum thermal resistor.

[0092] Reference Figures 1 to 6 , the temperature range of the temperature controller is 20℃~100℃.

[0093] 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 content.

[0094] 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.

[0095] Example 2

[0096] 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:

[0097] S1: In the glove box, assemble the outer shell, top gasket, bottom gasket, positive electrode sheet, negative electrode sheet, glass fiber, insulating sleeve, upper compression nut, lower compression nut, upper sealing ring and lower sealing ring into a battery body, and take it out of the glove box;

[0098] 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 positive electrode terminal slot 32 in the top gasket 22 and the negative electrode terminal slot 31 in the bottom gasket 29 to the charge and discharge system 6 respectively, and connect the connecting rod 21 to the battery assembly 8 through threaded engagement;

[0099] 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;

[0100] 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;

[0101] S5: The experimenter fixed the entire test device on the six-dimensional adjustment table of the spectrometer sample environment;

[0102] S6: The temperature controller is electrically connected to the heating rod 30 and the thermistor 33 respectively. 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 spectrometer scattering chamber via a data cable;

[0103] 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;

[0104] S8: Turn on the neutron beam line switch of the spectrometer to enable the conduction of the neutron beam;

[0105] S9: Start the experiment according to the predetermined experimental plan and save the relevant data.

[0106] 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:

[0107] 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 made of glass fiber, which will produce a tiny and chaotic neutron diffraction background after neutron diffraction, but has almost no effect on the regular neutron diffraction signals produced by the positive and negative electrodes. This is crucial 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. In this way, neutrons incident in this direction will be absorbed by the boron nitride and will not produce diffraction signals on the relevant materials.

[0108] 2. The connection device used is suitable for the general powder diffractometer and small-angle diffractometer of the China Spallation Neutron Source, and is also applicable to other spectrometers, avoiding the need for experimenters to repeatedly design supporting connection devices;

[0109] 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 tedious operations are required.

[0110] 4. When calibrating the position of the experimental sample, the time for aligning the sample 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 not change the sample position when replacing the positive or negative electrode, 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;

[0111] 5. The all-solid-state lithium-ion in-situ testing device used in the present invention has fewer components and is easy to produce and process. The battery device is assembled in a threaded and hanging manner, which is easy to operate and is conducive to its use in actual life and production. In addition, the clamping mechanism that maintains close contact with the current collector surface during battery charging and discharging is changed from the original spring to a threaded pre-compression structure, reducing the number of components of the battery device and making the overall device more compact.

[0112] 6. The all-solid-state lithium ion in-situ testing device of the present invention is sealed with O-rings, 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 electrodes themselves to the titanium-zirconium alloy gasket in contact with them, eliminating the influence of pores on the sealing performance;

[0113] 7. The all-solid-state lithium-ion in-situ testing device of the present invention is matched with a controllable temperature environment and an in-situ charge and discharge device, with a temperature range of 20 to 100°C, which meets the testing environment of most batteries;

[0114] 8. The operation of replacing the positive / negative electrode sheet and the positive / negative electrode sheet can be achieved by matching titanium-zirconium alloy gaskets of different thicknesses.

[0115] In the description of the present invention, it should be understood 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 should not be understood as limiting the present invention.

[0116] In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "connect," "fixed," etc. should be understood broadly. For example, they may refer to fixed connection, detachable connection, or integration; mechanical connection or electrical connection; direct connection or indirect connection through an intermediate medium; internal communication between two components or interaction between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention based on specific circumstances.

[0117] The above embodiments are merely specific embodiments of the present invention, and their descriptions are relatively specific and detailed. However, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make various modifications and improvements without departing from the scope of the present invention, and such obvious alternatives are all within the scope of protection of the present invention.

Claims

1. An all-solid-state lithium ion in-situ testing device, characterized by: The testing device is detachably mounted on the six-dimensional adjustment table of the spectrometer sample; the testing device includes a sample device, a temperature control system, a charge and discharge system, and a detector device; The sample device is detachably mounted on the six-dimensional adjustment platform of the spectrometer sample environment; the sample device includes a connecting assembly, a sample rod and a battery assembly; the connecting assembly is detachably mounted on the six-dimensional adjustment platform of the spectrometer sample; the battery assembly is connected to the connecting assembly through the sample rod; the battery assembly includes a top shell, a connecting rod, a battery body and a bottom shell; a through hole is provided on the top of the top shell for the connecting rod to extend outward from 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 pressing nut; the bottom shell is pressed against the lower part of the battery body by a lower pressing nut; the battery body is arranged between the top shell and the bottom shell; The temperature control system is arranged outside the sample device, and the temperature range of the temperature control system is 20°C to 100°C; The charging and discharging system is electrically connected to the sample device; The detector device is arranged outside the sample device.

2. The all-solid-state lithium ion in-situ testing device according to claim 1, characterized in that: The connecting assembly includes an annular connecting flange and a mounting flange for mounting the sample rod; The connecting assembly is detachably mounted on the spectrometer sample six-dimensional adjustment platform via a connecting flange; The mounting flange is mounted at the center of the circular ring of the connecting flange; The mounting flange is provided with a guide portion for facilitating the installation of the sample rod.

3. The all-solid-state lithium ion in-situ testing device according to claim 1, characterized in that: The battery body includes a 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 housing is pressed against the lower end of the link rod through an upper pressing nut, and the other end is pressed against the bottom housing through a lower pressing nut; The top gasket and the bottom gasket are detachably mounted in the housing and are disposed between the upper compression nut and the lower compression 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.

4. The all-solid-state lithium ion in-situ testing device according to claim 3, characterized in that: At least one sealing ring is respectively provided between the top gasket, the bottom gasket and the outer shell.

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

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