A full solid-state prototype battery reaction cell device using in-situ characterization of synchrotron soft x-rays

Abstract

The application discloses a kind of full solid-state prototype battery reaction cell device using in-situ characterization of synchrotron soft X-ray, belong to solid-state battery detection technical field;Reaction cell device includes top cover and support platform, window is opened in top cover and passes through up and down, light-transmitting window is arranged directly below window, inert metal film is deposited on light-transmitting window, positive electrode material can also be deposited on inert metal film, light-transmitting window allows synchrotron soft X-ray to pass through;The upper surface of support platform is provided with boss, first rubber ring and battery groove are arranged on boss, electrically-conductive elastic member, negative electrode material, solid-state electrolyte are sequentially placed in battery groove from bottom to top, solid-state electrolyte is in contact with light-transmitting window directly above it;The boss, first rubber ring, light-transmitting window seal the prototype battery surrounding.This reaction cell device can carry out in-situ synchrotron soft X-ray absorption spectroscopy and mass spectrum detection when full solid-state prototype battery is charged and discharged.

Description

Technical Field

[0001] This invention belongs to the field of solid-state battery testing technology, specifically relating to a prototype all-solid-state battery reaction cell device characterized in situ using synchrotron radiation soft X-rays. Background Technology

[0002] All-solid-state batteries, such as all-solid-state lithium-ion batteries, use non-flammable solid electrolytes instead of traditional organic liquid electrolytes, which is expected to fundamentally solve the safety problems of lithium batteries and potentially achieve higher energy density and longer cycle life. However, the performance of solid-state batteries is currently severely limited by the interface between the electrode and the solid electrolyte. This interface may suffer from poor contact, high interfacial impedance, complex interfacial side reactions, and the generation of gaseous products (such as O2, CO2, SO2, etc.) during electrode reactions, which will further deteriorate the interfacial contact and battery performance. Therefore, real-time, in-situ monitoring of the chemical reaction process at the electrode interface of all-solid-state batteries and its accompanying gas generation behavior is crucial for understanding the interface degradation mechanism of all-solid-state batteries, guiding interface optimization, and improving battery safety. Existing synchrotron radiation hard X-ray in-situ characterization techniques can achieve in-depth analysis of the bulk structure of battery materials, but the dynamic reaction process at the electrode surface still needs to be accurately detected using the high surface sensitivity of synchrotron radiation soft X-rays (photon energy range typically 124-1240 eV). While differential electrochemical mass spectrometry (DEMS) can effectively capture gas generation behavior during battery half-reactions and full-cell electrochemical cycling, it is currently not compatible with simultaneous joint detection using soft X-ray technology. Existing in-situ characterization techniques for liquid-phase reaction cells are limited to standalone synchrotron X-ray detection or standalone mass spectrometry detection; no reaction cell suitable for solid-state batteries has yet been found that can simultaneously perform in-situ soft X-ray detection and mass spectrometry. Furthermore, due to poor contact between the solid interfaces of different components in solid-state batteries and the low activity of solid electrolytes at room temperature, there is currently a lack of reaction cell devices suitable for in-situ synchrotron soft X-ray characterization and testing of all-solid-state batteries under ultra-high vacuum conditions. Summary of the Invention

[0003] To address the problems existing in the prior art, this invention proposes a reaction cell device for all-solid-state prototype batteries using in-situ characterization with synchrotron radiation soft X-rays. The purpose of this invention is to solve at least one of the many problems existing in the prior art, such as poor interface contact, inability to use synchrotron radiation soft X-rays for effective in-situ characterization and testing of all-solid-state batteries, and inability to be coupled with mass spectrometry.

[0004] The technical solution in this regard is as follows: A prototype solid-state battery reactor device for in-situ characterization using synchrotron radiation soft X-rays includes a top cover and a support platform, which are detachably connected by bolts. The top cover is made of insulating material, and the support platform is made of conductive material. A vertically penetrating window is provided on the top cover, and a light-transmitting window is located directly below the window. An inert metal film is deposited on the light-transmitting window, and a positive electrode material can also be deposited on the inert metal film. The light-transmitting window allows synchrotron radiation soft X-rays to pass through. A boss is provided on the upper surface of the support platform, and a first rubber ring and a battery slot are provided on the boss. A conductive elastic element, a negative electrode material, and a solid electrolyte are placed sequentially from bottom to top in the battery slot. The solid electrolyte is in contact with the light-transmitting window directly above it. The negative electrode material, solid electrolyte, and positive electrode material constitute the prototype full cell. When no positive electrode material is available, the negative electrode material, solid electrolyte, and inert metal film constitute the prototype half cell. The boss, the first rubber ring, and the light-transmitting window seal and surround the prototype battery.

[0005] Furthermore, an insulating ring is installed on the support platform, coaxially sleeved on the outside of the boss. A conductive washer is placed on the upper surface of the insulating ring. An insulating post protruding downwards is also provided on the lower surface of the insulating ring, passing through the support platform. A through hole is provided on the insulating post along its axial direction, and a conductive spring plunger is provided in the through hole. The top of the conductive spring plunger abuts against the lower surface of the conductive washer, so that the upper surface of the conductive washer makes conductive contact with the inert metal film of the light-transmitting window, thus leading out the positive electrode electrical signal of the prototype battery. A negative electrode lead is connected to the lower surface of the support platform, leading out the negative electrode electrical signal of the prototype battery. The positive and negative electrode signals of the prototype battery can be connected to an external battery testing system to perform charge and discharge operations on the prototype battery to test its electrical performance. At the same time as the battery is charging and discharging, synchrotron radiation soft X-rays pass through the light-transmitting window and reach the interface between the positive electrode material and the electrolyte. The material at the interface absorbs the soft X-rays and is excited to emit X-ray fluorescence. The X-ray fluorescence can be detected to obtain the in-situ X-ray absorption spectrum.

[0006] Optionally, a first air hole and a second air hole are provided on the support platform, with the upper openings of both the first air hole and the second air hole located inside the first rubber ring and on opposite sides of the battery compartment. A first air pipe hole and a second air pipe hole are respectively provided on the lower surface of the support platform, with the first air pipe hole communicating with the lower opening of the first air hole and the second air pipe hole communicating with the lower opening of the second air hole. A first air pipe is sealed and installed in the first air pipe hole, and a second air pipe is sealed and installed in the second air pipe hole. The first air pipe can be connected to an external gas cylinder, and the second air pipe can be connected to an external mass spectrometer. The gas cylinder can provide inert carrier gas or working gas to the prototype battery in the battery compartment. During the charging and discharging process of the prototype battery, if there is gas generation, the generated gas will be introduced into the mass spectrometer by the inert carrier gas, thereby identifying and analyzing the gas type.

[0007] Optionally, a heating element is installed on the lower surface of the support platform. The heating element heats the prototype battery through heat conduction, which can improve the reactivity of the solid-state battery and evaluate the thermal safety of the battery.

[0008] Furthermore, the reaction cell device also includes a base made of insulating material. The support platform is detachably connected to the base by bolts, and a sealing rubber ring A is provided between the support platform and the base. The base has vertically penetrating holes for a positive electrode lead-out, a negative electrode lead-out, a heating wire lead-out, a third gas pipe hole, and a fourth gas pipe hole. A positive electrode lead-out bolt is installed in the positive electrode lead-out hole, which compresses the spring plunger to bring out the positive electrode signal of the prototype battery. Sealing rubber rings a and b are respectively provided around the upper and lower openings of the positive electrode lead-out hole. The insulating base provides an insulating environment for the reaction cell and facilitates the exit of various leads and gas pipes. The sealing design of multiple rubber rings ensures that the reaction cell does not leak when in a vacuum environment.

[0009] Furthermore, a transition rod is also installed on the base. The transition rod is a hollow structure, and a rubber ring B seals the connection between the transition rod and the base. The design of the transition rod facilitates the connection between the reaction tank device and the experimental chamber.

[0010] Preferably, the light-transmitting window is a silicon nitride window with a silicon wafer as the substrate, and the inert metal film deposited on it is a Pt thin film with a thickness of 5-10 nm.

[0011] Preferably, the conductive elastic element is a conductive sheet or a conductive spring.

[0012] Preferably, the all-solid-state prototype battery is an all-solid-state lithium-ion prototype battery, the positive electrode material contains lithium iron phosphate, the negative electrode material is lithium sheet, and the solid electrolyte allows lithium ions to pass through.

[0013] Furthermore, the insulating material used for the top cover is polyetheretherketone, and the conductive material used for the support platform can be gold, silver, copper, aluminum, etc., with copper being preferred.

[0014] Beneficial effects: (1) The all-solid prototype battery reaction cell device provided by the present invention is composed of negative electrode material, solid electrolyte and positive electrode material / Pt to form an all-solid prototype full cell / half cell. The prototype battery is squeezed by the elastic force of the conductive elastic element, so that the interfaces of the various solid components of the prototype battery can be in good contact. At the same time, the positive electrode signal of the battery is effectively extracted by the conductive spring plunger extrusion and compression of the conductive gasket and the inert metal film on the light-transmitting window. The negative electrode signal of the battery is effectively extracted by the all-copper support platform and the conductive elastic element. The positive and negative electrode extraction methods of the battery are ingenious. While the prototype battery is charging and discharging, the synchrotron radiation soft X-rays injected from the light-transmitting window reach the interface between the electrode material and the solid electrolyte. The chemical reaction at the battery electrode interface can be detected in situ by testing the absorption spectrum of the synchrotron radiation soft X-rays and the dynamic changes of the absorption spectrum. (2) The support platform is made of copper material, which utilizes copper’s good electrical conductivity and thermal conductivity. The device has a heating element embedded in the lower surface of the support platform to heat the support platform and thus control the working temperature of the prototype battery. Because the activity of solid electrolyte is low at room temperature, increasing the temperature can improve the activity of the prototype battery and make it easier to collect the change signal of the absorption spectrum. At the same time, the addition of a temperature variable makes the scientific research on the prototype battery more comprehensive. For example, it can evaluate its thermal safety performance and / or the electrical performance and chemical changes of the battery at different temperatures. (3) This reaction cell device is equipped with an air inlet and an air outlet. The inert carrier gas can be used to introduce the gas that may be generated during the charging and discharging process of the prototype battery into the online mass spectrometer, and the possible gas generation behavior of the prototype battery can be monitored simultaneously. The charging and discharging behavior of the battery can be characterized in conjunction with the X-ray absorption spectrum. On the other hand, the air inlet can also be used to introduce working gas to study the effect of different working gases on the charging and discharging performance of the prototype battery. Moreover, the ventilation range of this device is strictly sealed by the sealing rubber ring, which will not affect or damage the high vacuum state of the synchrotron radiation beamline and the experimental chamber. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the overall assembly structure of the reaction tank device of the present invention.

[0016] Figure 2 This is a schematic diagram of the explosion state of the reaction tank device of the present invention.

[0017] Figure 3 This is a schematic diagram of the top cover of the reaction tank; where (a) is the top view and (b) is the bottom view.

[0018] Figure 4 This is a schematic diagram of the insulating ring structure.

[0019] Figure 5 This is a schematic diagram of the support platform; where (a) is the top view and (b) is the bottom view.

[0020] Figure 6 This is a schematic diagram of the base of the reaction tank; where (a) is the top view and (b) is the bottom view.

[0021] Figure 7 yes Figure 1 A cross-sectional view.

[0022] Figure 8 yes Figure 1 Another sectional view.

[0023] Figure 9 This is a schematic diagram of the prototype battery's structure and in-situ testing.

[0024] Figure 10 This is a schematic diagram showing the reaction tank installed at the experimental station.

[0025] Figure 11 This is a test workflow diagram.

[0026] Figure 12 It is the K-edge absorption spectrum of fluorine in the prototype battery before and after charging and discharging.

[0027] Figure 13 This is the voltage-time curve of the prototype battery LiFePO4 / electrolyte / Li.

[0028] Figure 14 These are mass spectra of the prototype battery before and after charging and discharging.

[0029] The markings in the diagram are: 1 top cover, 2 light-transmitting window, 3 insulating ring, 4 support platform, 5 base, 7 heating element, 8 beam line, 9 experimental chamber, and 10 reaction cell. 11 First bolt, 12 Window, 13 Ring groove, 14 Frustum, 15 First groove; 31 Conductive washer, 32 Conductive spring plunger, 33 Tabletop, 34 Insulating post; 41 Second bolt, 42 First rubber ring, 43 First cylindrical boss, 44 First annular groove, 45 Second cylindrical boss, 46 Battery slot, 47 First air hole, 48 Second air hole, 49 Second groove, 401 Negative terminal blind hole, 402 Insulating post through hole, 471 First air pipe hole, 481 Second air pipe hole. 51 Positive electrode lead-out hole, 52 Heating wire lead-out hole, 53 Negative electrode lead-out hole, 54 Third air pipe hole, 55 Fourth air pipe hole, 56 Large rubber ring A, 57 Small rubber ring a, 58 Positive electrode lead-out bolt, 59 Large rubber ring B, 571 Small rubber ring b. 61 Silicon wafer, 62 Silicon nitride thin film, 63 Inert metal thin film, 64 Positive electrode material, 65 Solid electrolyte, 66 Negative electrode material, 67 Conductive elastic element, 68 Negative electrode; 71 Heating element cover; 72 Heating wire; 81 Gate valve; 91 Fluorescence detector; 101 Transition rod; 102 Flange. Detailed Implementation

[0030] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and embodiments.

[0031] The example uses the testing of an all-solid-state lithium-ion battery as an example; for other solid-state batteries such as sodium-ion batteries and zinc-ion batteries, adjustments can be made according to actual needs.

[0032] Example 1 A prototype all-solid-state battery reactor device characterized in situ using synchrotron soft X-rays, such as Figures 1-8 As shown, the reaction tank 10 mainly includes a top cover 1, a light-transmitting window 2, an insulating ring 3, a support platform 4, and a base 5. The support platform 4 is located between the top cover 1 and the base 5. All three are cylindrical in shape and are coaxially arranged. The top cover 1 and the support platform 4 are detachably connected by six first bolts 11, and the support platform 4 and the base 5 are detachably connected by six second bolts 41. The top cover 1, the insulating ring 3, and the base 5 are all made of insulating materials such as polyetheretherketone (PEEK), and the support platform 4 is made of copper, which has excellent electrical and thermal conductivity.

[0033] The structure of top cover 1 is as follows Figure 3 As shown, a vertically extending window 12 is provided axially at the center of the top cover. To facilitate the incident of synchrotron radiation soft X-rays and the emission of generated X-ray fluorescence, the window 12 is flared, with a larger outer diameter and a smaller inner diameter. An annular groove 13 and a frustum 14 are provided on the back of the top cover. The frustum 14 is located at the center of the top cover, and there is a certain distance between the lower surface of the frustum 14 and the lower surface of the top cover 1. A first groove 15 is provided centrally on the lower surface of the frustum 14. The shape of the first groove can be circular, square, or rectangular; the first groove shown in the figure is a square with a side length of 10 mm. A light-transmitting window 2, matching the size of the first groove, is placed inside the first groove 15. The area of ​​the light-transmitting window 2 is larger than the area inside the window 12. The light-transmitting window 2 covers the window 12 from below, and is located directly below the window, allowing soft X-rays to pass through.

[0034] like Figure 9As shown, the light-transmitting window used in this invention is a silicon nitride thin film window deposited on a silicon wafer as a support. Silicon nitride is an inorganic non-metallic material with high strength, high hardness, high heat resistance, high corrosion resistance, and a low coefficient of thermal expansion. It has low absorption of soft X-rays, allowing soft X-rays to pass through. First, a large-area (e.g., 10mm × 10mm) uniform and dense silicon nitride thin film 62 of a certain thickness is formed on the substrate silicon wafer 61 using methods such as chemical vapor deposition (CVD) or physical vapor deposition (PVD). Then, a small central area of ​​the silicon wafer is etched or etched to remove excess silicon material, leaving only the etched area of ​​silicon nitride thin film to form a self-supporting window (e.g., a 3mm diameter area), thus forming the so-called silicon nitride thin film window. The silicon wafer substrate used in this invention has a size of 10mm × 10mm and a thickness of 200μm. The thickness of the silicon nitride thin film can be adjusted according to experimental requirements; in this example, the thickness of the silicon nitride thin film is approximately 100nm. Meanwhile, to meet the battery's conductivity requirements, an inert metal film 63 is deposited on the silicon nitride film of the entire light-transmitting window as a positive electrode current collector, such as Pt, Au, or Ag. In this example, Pt is chosen as the inert metal film, with a thickness of 5-10 nm. This thickness of platinum satisfies the battery's conductivity requirements while allowing most of the soft X-rays to pass through. A layer of positive electrode material 64 can be deposited or prepared in the central region of the inert metal film of the light-transmitting window. The area of ​​the positive electrode material must be larger than the area of ​​the self-supporting window of the silicon nitride film, while being smaller than the area of ​​the inert metal film. This ensures that the outer inert metal film on the light-transmitting window is not covered by the positive electrode material and remains exposed, thus facilitating the extraction of the positive electrode signal.

[0035] like Figure 5 As shown, a first cylindrical boss 43 is provided at the center of the upper surface of the support platform 4. A first annular groove 44 and a second cylindrical boss 45 are provided on the surface of the first cylindrical boss 43. The first annular groove 44 surrounds the second cylindrical boss 45. The surfaces of the first cylindrical boss and the second cylindrical boss are coplanar. A first rubber ring 42 is provided in the first annular groove 44. The area enclosed by the first rubber ring is smaller than the area of ​​the light-transmitting window, and the thickness of the first rubber ring is greater than the depth of the first annular groove. When the reaction tank top cover 1 and the support platform 4 are fastened together, the first... A rubber ring 42 is centered in contact with the light-transmitting window 2 directly above it to ensure a tight seal between the first rubber ring and the light-transmitting window; a battery slot 46 is provided on the surface of the second cylindrical protrusion 45, and a prototype battery is placed inside the battery slot. Specifically, a conductive elastic element 67, a negative electrode material 66, and a solid electrolyte 65 are placed sequentially from bottom to top inside the battery slot 46. The solid electrolyte 65 is in contact with the positive electrode material 64 attached to the light-transmitting window directly above it; the negative electrode material 66, the solid electrolyte 65, and the positive electrode material 64 constitute the prototype battery (see...). Figure 9The support platform 4, the first rubber ring 42, and the light-transmitting window 2 seal and surround the prototype battery, and the first rubber ring 42 insulates and isolates the light-transmitting window 2 from the first cylindrical protrusion 43 of the support platform. The conductive elastic element 67 can be a spring or a group of springs, or a wave-shaped elastic plate or sheet. The elastic element can conduct electricity to transmit current to the negative electrode 68 (in this example, the support platform 4 as a whole serves as the negative electrode of the battery). At the same time, the elastic element deforms under pressure to generate elastic force. This elastic force makes the interfaces between the negative electrode material, solid electrolyte, and positive electrode material that make up the prototype battery press against each other, improves the contact state between the solid interfaces of different components, and enables the prototype battery to work normally.

[0036] In order to effectively extract the positive electrode current generated by the inert metal film 63 of the above-mentioned prototype battery, an insulating ring 3 (see above) is also installed on the support platform 4. Figure 4 The insulating ring 3 is coaxially sleeved on the outside of the first cylindrical boss 43. The outer diameter of the insulating ring is less than or equal to the outer diameter of the annular groove 13 on the top cover. A recessed platform 33 is provided on the upper surface of the insulating ring 3, and a conductive washer 31 is placed on the platform 33. When the reaction tank top cover 1 and the support platform 4 are fastened together, the insulating ring 3, the conductive washer 31, and the first cylindrical boss 43 are all embedded in the annular groove 13 of the reaction tank top cover. The insulating ring 3 serves as an insulating and insulating window and a support platform to prevent short circuit between the positive and negative poles. A downwardly protruding insulating post 34 is also provided on the lower surface of the insulating ring 3. The insulating post 34 passes downward through the insulating post through hole 402 on the support platform. A through hole is provided along its axial direction inside 34. A conductive spring plunger 32 is installed in the through hole by threaded connection. The top of the conductive spring plunger 32 can elastically extend and retract to press against the lower surface of the conductive washer 31, so that the upper surface of the conductive washer 31 can effectively make electrical contact with the outer inert metal film 63 on the light-transmitting window, thereby leading out the positive electrode electrical signal of the prototype battery. The conductive washer 31 is used to conduct positive electrode current on the one hand, and also serves to protect the light-transmitting window 2 from breakage on the other hand. Because the light-transmitting window 2 is based on a silicon wafer, it is easy to break. If the conductive washer 31 is not provided and the top of the conductive spring plunger 32 directly presses against the Pt-plated layer of the light-transmitting window, the light-transmitting window will easily break. Figure 4Only one insulating post 34 is shown on the insulating ring 3. However, three insulating posts can also be evenly spaced on the lower surface of the insulating ring 3, each containing a conductive spring plunger. The tops of the three spring plungers together press against the conductive washer, improving contact between the conductive washer and the inert metal film. A negative electrode blind hole 401 is provided on the lower surface of the support platform 4 for connecting the negative electrode lead, which leads out the negative electrode electrical signal of the prototype battery. After the positive and negative electrodes of the prototype battery are connected to the battery performance testing system, the charging and discharging behavior of the prototype battery can be controlled. During the charging and discharging process of the prototype battery, synchrotron radiation soft X-rays incident through the light-transmitting window reach the interface between the positive electrode material and the solid electrolyte. Based on the collected X-ray absorption spectrum and its dynamic changes, chemical changes at the battery interface can be detected. Figure 9 The prototype battery shown is a prototype full cell; if no positive electrode material is attached to the inert metal film of the light-transmitting window, that is, the inert metal film of the light-transmitting window is in direct contact with the solid electrolyte below it, then the negative electrode material, the solid electrolyte, and the inert metal film constitute a prototype half cell; the reaction cell device described in this application can also be used for performance studies of prototype half cells. The prototype battery described in this application may include prototype full cells and / or prototype half cells.

[0037] One of the core components of an all-solid-state battery is the solid electrolyte. However, in existing technologies, the activity of solid electrolytes at room temperature is relatively low, which may lead to poor charge-discharge behavior of the aforementioned prototype battery at room temperature. To improve the performance of the prototype battery, this embodiment can also provide a second groove 49 on the lower surface of the support platform 4, and install a heating element 7 in the second groove 49. The heating element can be a ceramic heating element, and the heating element 7 is fixed by a heating element cover 71. The heat generated by the heating element 7 is first conducted to the copper-based support platform 4, and then transferred from the support platform 4 to the prototype battery and its solid electrolyte 65. After the solid electrolyte is heated, its activity increases, and the performance of the prototype battery will also change or improve. The heating temperature can be controlled by the output power of the heating power supply connected to the heating wire 72. Alternatively, a thermocouple can be installed on the lower surface of the support platform 4 to monitor its temperature in real time and use PID for precise temperature control. The heating temperature control function in this example can be used to study the charge-discharge behavior of the prototype battery at different temperatures and the X-ray absorption spectrum under these conditions.

[0038] To effectively detect potential gas generation during the charging and discharging of the prototype battery, this embodiment also provides a first vent 47 and a second vent 48 that extend vertically through the second cylindrical boss 45 on the support platform 4. On the upper surface of the second cylindrical boss 45, the upper openings of the first vent 47 and the second vent 48 are located on opposite sides of the battery slot 46 and surrounded by a first rubber ring 42. On the lower surface of the support platform 4, a first vent hole 471 and a second vent hole 481 are respectively provided. The first vent hole 471 communicates with the lower opening of the first vent 47, and the second vent hole 481 communicates with the lower opening of the second vent 48. A first vent pipe is sealed and installed inside the first vent hole 471, and a second vent pipe is sealed and installed inside the second vent hole 481. The first vent pipe can be configured as an inlet pipe and the second vent pipe as an outlet pipe, or vice versa. Taking the first vent pipe as an inlet pipe and the second vent pipe as an outlet pipe as an example, the first vent pipe is connected to an inert gas (Ar) cylinder, and the second vent pipe is connected to an online mass spectrometer. Ar gas enters the battery compartment 46 through the first vent 47. Assuming that gas is generated during the charging and discharging process of the prototype battery, the generated gas is carried by the Ar gas and extracted through the second vent 48 to the online mass spectrometer, where it is identified as the specific type of gas. Because the Ar gas entering the battery compartment is sealed by the first rubber ring 42, it will not leak into the vacuum environment of the experimental chamber and will not disrupt the vacuum. In this example, synchrotron radiation soft X-ray absorption spectroscopy and mass spectrometry can also be used for in-situ synergistic characterization of solid-state batteries. Of course, the types of gas introduced into the battery compartment 46 are not limited to inert gases. For different types of solid-state batteries, such as sodium-ion batteries, zinc-ion batteries, and aluminum-ion batteries, active reactive gases can also be introduced as needed.

[0039] The heating and temperature control functions and the ventilation / mass spectrometry function mentioned above can also be integrated together.

[0040] The support platform 4 is detachably mounted on the insulated base 5, which provides insulation support for the entire reaction tank. The base 5 is provided with a through-hole 51 for the positive electrode wire, a through-hole 52 for the negative electrode wire, a through-hole 53 for the heating wire, a third gas pipe hole 54, and a fourth gas pipe hole 55. If necessary, a thermocouple wire lead-out hole can also be provided on the base 5, and of course, the thermocouple wire lead-out hole can also be shared with other lead-out holes. The third air pipe hole 54 corresponds to the first air pipe hole 471 on the lower surface of the support platform 4, and the fourth air pipe hole 55 corresponds to the second air pipe hole 481 on the lower surface of the support platform 4. A small rubber ring a 57 is coaxially arranged around the positive electrode lead-out hole 51 on the upper surface of the base 5, and a small rubber ring b 571 is also coaxially arranged around the positive electrode lead-out hole 51 on the lower surface of the base 5. A positive electrode lead-out bolt 58 is installed inside the positive electrode lead-out hole 51, which presses and seals the small rubber ring b, and presses the conductive contact spring plunger to bring out the positive electrode signal of the prototype battery. A large rubber ring A 56 is also provided between the base 5 and the support platform 4 for sealing. When the base 5 and the support platform 4 are fastened together, the large rubber ring A and the small rubber rings a / b simultaneously provide a sealing function. The small rubber rings a and b prevent air leakage from the spring plunger and the positive electrode lead-out bolt, while the large rubber ring A prevents air leakage from the first and second air pipes, thus preventing damage to the vacuum of the experimental chamber. The rubber rings in this application are all O-rings, and the material can be fluororubber, which has a certain degree of elasticity and flexibility, can seal under pressure, and is resistant to high temperature, corrosion, and has good insulation properties, making it suitable for ultra-high vacuum environments.

[0041] To facilitate the installation of the reaction tank 10 at the experimental station, a matching transition rod 101 was also designed, such as... Figure 10 As shown. A flange 102 is provided at the left end of the transition rod 101, and the transition rod 101 is detachably and sealed to the experimental chamber 9 through the flange 102. The right end of the transition rod 101 extends into the interior of the experimental chamber 9 and is detachably and sealed to the bottom surface of the base 5 of the reaction cell 10 through a large rubber ring B 59. The transition rod 101 is hollow, and various leads and gas pipes leading out from the base 5 of the reaction cell pass through the interior of the transition rod 101 and lead out to the atmospheric environment outside the experimental chamber 9. During operation, the interior of the experimental chamber 9 is in a vacuum state. The experimental chamber 9 is also equipped with a fluorescence detector 91. The experimental chamber 9 is connected to the beamline 8, and a gate valve 81 is provided on the beamline 8 to isolate the vacuum between the experimental chamber and the beamline. When the gate valve 81 is opened, the synchrotron radiation light emitted from the electron storage ring is led out through the beamline 8 and can then irradiate the reaction cell inside the experimental chamber.

[0042] The following example of an all-solid-state lithium-ion battery illustrates the use of the above-mentioned reaction cell device and the in-situ testing method.

[0043] A synchrotron radiation soft X-ray in-situ testing method for an all-solid-state lithium-ion prototype battery includes the following steps: S1. Prepare a light-transmitting window 2 with a silicon wafer as the substrate and a silicon nitride thin film deposited on it. Then, deposit a 5-10 nm thick Pt thin film on the silicon nitride thin film of the light-transmitting window 2 as a current collector to meet the conductivity requirements of the prototype half-cell. Of course, according to research needs, a lithium iron phosphate cathode material layer can also be prepared on the Pt thin film at the center of the light-transmitting window, ensuring that the Pt thin film at the edge of the light-transmitting window is not covered by the cathode material. This can meet the requirements for constructing a prototype full cell. The cathode material layer can be prepared by the following method: prepare a DMF solution by mixing lithium iron phosphate, conductive carbon black and PVDF in a ratio of 8:1:1, drop it onto the center surface of the light-transmitting window 2, and then place it in an oven at 60 degrees Celsius for 12 hours to dry it for later use.

[0044] S2, In a glove box filled with inert gas Ar, reaction tank 10 is assembled, specifically including: S2.1 Prepare support platform 4, and install heating element 7, negative lead wire, first air pipe and second air pipe on the back of support platform 4. Thermocouple can also be installed as needed. S2.2 Next, prepare the base 5, install the large rubber ring A56 and the small rubber ring a57 on the base 5, then align the support platform 4 in S2.1 with the base 5 and fasten them together, so that the heating wire, negative lead wire, first air pipe, second air pipe, thermocouple wire, etc. pass through the corresponding through holes of the base 5. Then use bolts to fix the support platform 4 to the base 5, and press the large rubber ring A56 and the small rubber ring a57 to achieve the sealing effect. S2.3 Next, an insulating ring 3 is installed on the support platform 4, a conductive washer 31 is placed on the insulating ring 3, and a first rubber ring 42 is placed in the first annular groove 44. S2.4, then place the conductive elastic element 67, lithium sheet negative electrode material 66, and solid electrolyte 65 that allows lithium ions to pass through in sequence in the battery compartment 46. The solid electrolyte can be a PVDF-based solid electrolyte, and the height of the upper surface of the solid electrolyte 65 is required to be slightly higher than the height of the first rubber ring 42. Next, align the light-transmitting window 2 in S1 with the first groove 15 embedded in the top cover 1. The four corners of the light-transmitting window 2 can be fixed with vacuum conductive tape. Then, fasten the top cover 1 onto the support platform 4 so that the Pt film or lithium iron phosphate positive electrode material layer on the light-transmitting window is in direct contact with the solid electrolyte. At this time, the top cover 1 presses down on the light-transmitting window 2, and the light-transmitting window 2 presses down on the solid electrolyte 65 and the first rubber ring 42. Then, fix the top cover 1 and the support platform 4 together with bolts. After the first rubber ring 42 is compressed, it surrounds and seals the prototype battery. The prototype battery presses down on the conductive elastic element, causing it to deform elastically and generate appropriate elastic force. This elastic force allows the interface between the positive and negative electrode materials and the solid electrolyte to make good contact. S2.5 Next, insert the conductive spring plunger 32 into the positive electrode lead-out hole 51 of the base 5, and place the small rubber ring b571. Tighten the positive electrode lead-out bolt 58 to press and seal the small rubber ring b571. The bolt 58 pushes the conductive spring plunger 32 upward, and the top of the conductive spring plunger 32 presses against the conductive washer 31, so that the conductive washer 31 makes conductive contact with the Pt film on the light-transmitting window 2. The bolt 58 connects the positive electrode lead, completing the lead-out of the positive electrode signal of the prototype battery. S2.6, Place a large rubber ring B59 on the back of the base of the reaction tank 10 to seal and fix the reaction tank 10 to the transition rod 101, and make the first gas pipe, the second gas pipe and various leads of the reaction tank pass through the transition rod 101 to seal the end of the gas pipe; the assembly of the reaction tank and the transition rod is completed.

[0045] S3. Take out the assembled reaction cell and transition rod from the glove box, and install the transition rod onto the experimental chamber 9 through flange 102, so that the reaction cell extends into the experimental chamber 9; evacuate the experimental chamber 9; at the same time, connect the first gas tube to the Ar gas cylinder, connect the second gas tube to the sample inlet of the mass spectrometer, connect the heating wire and thermocouple wire to the heating power supply with PID control, and connect the positive and negative leads of the prototype battery to the battery testing system.

[0046] S4, Data Acquisition: When the vacuum level inside experimental chamber 9 reaches a certain level, for example, better than 10... -6 After mbar, the gate valve 81 is opened, allowing synchrotron radiation soft X-rays from beamline 8 to irradiate the reaction cell inside the experimental chamber. The synchrotron radiation soft X-rays pass through the light-transmitting window and are absorbed at the interface between the cathode material and the solid electrolyte. Simultaneously, the emitted X-ray fluorescence is received by the fluorescence detector 91 inside the experimental chamber 9. After data processing, the X-ray absorption spectrum is obtained. Simultaneously or subsequently, the battery testing system is activated to charge and discharge the prototype battery. During or before and after charging and discharging, Ar gas is used as the carrier gas, and the gas production behavior of the prototype battery can be monitored synchronously and in real-time using a mass spectrometer. Depending on research needs, the heating system can also be activated to heat the prototype battery, studying its operating state, changes in the X-ray absorption spectrum, and mass spectrometry signals at different temperatures. Figure 12 The changes in the K-edge absorption spectrum of fluorine in the prototype battery before and after charge and discharge are shown. Figure 13 The charge-discharge curves of the prototype battery are shown. Figure 14 The mass spectra before and after charging and discharging are shown.

[0047] By utilizing synchrotron radiation soft X-ray in-situ characterization technology, the evolution of key information such as the valence state of each element during battery charging and discharging can be monitored in real time, thereby deriving the dynamic evolution process of the electrolyte-electrode interface. For example... Figure 12Taking fluorine (F) as an example: before the battery undergoes charge-discharge cycles, the detected F element characteristic signal corresponds exactly to the characteristic signal of polyvinylidene fluoride (PVDF); after the charge-discharge cycles are completed, the F element characteristic signal corresponding to lithium fluoride (LiF) is detected on the electrode surface. The above signal changes directly prove that a solid electrolyte interphase (SEI layer) has been formed on the electrode surface during the charge-discharge process.

[0048] Example 2 The difference between the reaction cell structure in this example and that in Example 1 is that the conductive elastic element in the battery compartment 46 in Example 1 is replaced with a force-controlled electric actuator, and the control line of the force-controlled electric actuator is sealed downwards, leading out of the support platform 4 and passing through the base 5. A force-controlled electric actuator is a commonly used industrial electric actuator capable of precisely controlling the pushing force. It typically consists of a housing, lead screw, push rod, nut, motor, and force sensor. Its working principle is that the motor drives the lead screw to rotate, causing the nut to slide along the length of the lead screw, thereby driving the push rod to extend or retract. The force sensor monitors the force applied by the push rod in real time and feeds the signal back to the motor to achieve precise force control. In this example, the force-controlled electric actuator supports and compresses the negative lithium electrode sheet. The negative lithium electrode sheet maintains electrical conductivity with the support platform throughout the compression displacement process. By controlling the force applied to the force-controlled electric actuator, the interfaces of the solid components of the prototype battery can be subjected to precisely quantitative different pressure states. Under these quantitatively different pressure states, the charge-discharge performance of the battery and in-situ synchrotron radiation and mass spectrometry characterization are studied.

[0049] In summary, the key innovations of this invention include, but are not limited to, its in-situ simultaneous characterization capability, enabling simultaneous synchrotron radiation soft X-ray spectroscopy analysis of interfacial chemistry and mass spectrometry detection of gas generation behavior during solid-state lithium battery operation. This technological breakthrough provides a crucial experimental tool for in-depth research into the dynamic mechanisms of battery interface evolution and battery safety analysis. Figure 11 As shown, the specific tests that the device of the present invention can perform include the following: (1) Synchrotron radiation X-ray absorption spectroscopy combined with mass spectrometry: The absorption spectrum can obtain real-time evolution information of element valence state and coordination structure in the interface region of solid electrolyte / electrode material during charge and discharge cycles, as well as the type and concentration of gaseous products that may be generated inside the battery as a function of time or potential.

[0050] (2) By changing the type of carrier gas, the influence of different gas environments on the electrochemical behavior of the battery can be explored.

[0051] (3) This device, through the functional design of heating ceramic plates, can accurately control the working temperature of the battery, thereby enabling systematic research on the reaction process of solid lithium batteries in a wide temperature range, as well as a comprehensive analysis of thermal safety.

[0052] (4) The charging and discharging performance of the battery was studied by changing the internal pressure state of the prototype battery.

[0053] In summary, the construction of the reaction cell device of this invention can significantly improve the research level on core scientific issues such as the interfacial reaction mechanism, interfacial gas generation and thermal safety of all-solid-state batteries, and powerfully promote the iterative development of the design and development of high-performance solid electrolyte materials and interface optimization strategies.

Claims

1. A prototype all-solid-state battery reactor device characterized in situ using synchrotron soft X-ray characterization, characterized in that, It includes a top cover and a support platform, which are detachably connected by bolts; the top cover is made of insulating material and the support platform is made of copper. A vertically extending window is provided on the top cover, and a light-transmitting window is provided directly below the window. An inert metal film is deposited on the light-transmitting window, and a positive electrode material can also be deposited on the inert metal film. The light-transmitting window allows synchrotron radiation soft X-rays to pass through. A boss is provided on the upper surface of the support platform. A first rubber ring and a battery slot are provided on the boss. A force-controlled electric push rod, a negative electrode material, and a solid electrolyte are placed sequentially from bottom to top in the battery slot. The solid electrolyte is in contact with the light-transmitting window directly above it. The force-controlled electric push rod supports and compresses the negative electrode material. The negative electrode material is electrically connected to the support platform. The negative electrode material, the solid electrolyte, and the positive electrode material constitute the prototype full cell. When there is no positive electrode material, the negative electrode material, the solid electrolyte, and the inert metal film constitute the prototype half cell. The boss, the first rubber ring, and the light-transmitting window seal and surround the prototype battery. A heating element is installed on the lower surface of the support platform; The in-situ characterization of soft X-rays by synchrotron radiation is performed by in-situ measurement of soft X-ray absorption spectrum using fluorescence mode. An insulating ring is installed on the support platform, and the insulating ring is coaxially sleeved on the outside of the boss. A conductive washer is placed on the upper surface of the insulating ring. An insulating post protruding downward is also provided on the lower surface of the insulating ring. The insulating post passes downward through the support platform. A through hole is provided on the insulating post along its axial direction. A conductive spring plunger is provided in the through hole. The top of the conductive spring plunger abuts against the lower surface of the conductive washer, so that the upper surface of the conductive washer is electrically connected to the inert metal film of the light-transmitting window, so as to lead out the positive electrode electrical signal of the prototype battery. A negative electrode lead is connected to the lower surface of the support platform, and the negative electrode lead leads out the negative electrode electrical signal of the prototype battery. The reaction tank device also includes a base made of insulating material. The support platform is detachably connected to the base by bolts, and a sealing rubber ring A is provided between the support platform and the base. The base has a through-hole for a positive electrode wire, a negative electrode wire, a heating wire, a third gas pipe, and a fourth gas pipe. A positive electrode wire lead-out bolt is installed in the positive electrode wire lead-out hole. The positive electrode wire lead-out bolt compresses the spring plunger to bring out the positive electrode signal of the prototype battery. A sealing rubber ring a and a rubber ring b are respectively provided around the upper and lower openings of the positive electrode wire lead-out hole. A transition rod is also installed on the base. The transition rod is a hollow structure and is sealed between the transition rod and the base by a rubber ring B. The transition rod is detachably and sealed to the experimental chamber through a flange. During operation, the experimental chamber is in a vacuum state. Various leads and air pipes led out from the base pass through the inside of the transition rod and are led out to the atmospheric environment outside the experimental chamber. The light-transmitting window is a silicon nitride window with a silicon wafer as the substrate, and the inert metal film deposited on it is a Pt thin film with a thickness of 5-10 nm.

2. The all-solid-state prototype battery reactor device characterized in situ using synchrotron soft X-rays according to claim 1, characterized in that, A first air hole and a second air hole are provided on the support platform, which are connected vertically. The upper openings of the first air hole and the second air hole are both located inside the first rubber ring and are located on both sides of the battery slot. A first air pipe hole and a second air pipe hole are respectively provided on the lower surface of the support platform. The first air pipe hole is connected to the lower opening of the first air hole, and the second air pipe hole is connected to the lower opening of the second air hole. A first air pipe is installed in the first air pipe hole, and a second air pipe is installed in the second air pipe hole. The first air pipe can be connected to an external gas cylinder, and the second air pipe can be connected to an external mass spectrometer.

3. The all-solid-state prototype battery reactor device for in-situ characterization using synchrotron soft X-rays according to claim 1, characterized in that, The all-solid-state prototype battery is an all-solid-state lithium-ion prototype battery. The positive electrode material contains lithium iron phosphate, the negative electrode material is lithium sheet, and the solid electrolyte allows lithium ions to pass through.

4. The all-solid-state prototype battery reactor device characterized in situ using synchrotron soft X-rays according to claim 1, characterized in that, The insulating material used for the top cover is polyetheretherketone.

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