All-solid-state battery in-situ cell adapted to synchrotron resonance soft X-ray scattering beamlines

Abstract

This invention relates to the field of in-situ characterization of solid-state batteries, specifically an all-solid-state battery in-situ cell adapted to synchrotron radiation resonance soft X-ray scattering beamlines. The cell includes a main body composed of an upper cell, a lower cell, and a middle cell. The upper and lower cells share a first light-transmitting aperture. A battery housing mechanism includes a receiving slot in the middle of the middle cell, within which a battery assembly is housed. An electrical connection mechanism includes a positive conductive post embedded in the upper cell and a negative conductive post embedded in the lower cell. A temperature monitoring mechanism includes mounting slots on opposite sides of the middle and lower cells, where thermocouples are installed. This in-situ cell exhibits strong testing stability, and its ultra-thin structure meets the penetration requirements of RSoXS soft X-rays. It allows for simultaneous acquisition of multiple parameters, enabling simultaneous monitoring of voltage, current, temperature, and scattering signals.

Description

Technical Field

[0001] This invention relates to the field of in-situ characterization of solid-state batteries, specifically to an all-solid-state battery in-situ cell adapted to a synchrotron radiation resonance soft X-ray scattering beamline. Background Technology

[0002] With the deepening research on the dynamic evolution of solid-state battery interfaces and ion transport mechanisms, synchrotron radiation technology has become a key characterization method due to its advantages of high resolution and element specificity. Among them, the resonant soft X-ray scattering beamline (RSoXS, energy range 240-700 eV, spatial resolution 5-500 nm) places specific demands on the transmittance, multi-parameter synchronization, and vacuum compatibility of in-situ testing devices. However, existing synchrotron radiation-compatible in-situ testing devices for solid-state batteries have not been customized for the technical parameters of RSoXS beamlines. In the prior art, patents with publication numbers CN119290987A, CN120722015A, CN110412013A, CN208818663U, CN223597566U, and CN208818663U all disclose corresponding technologies. However, the following problems still exist with the aforementioned prior art: 1. Mismatch between light transmittance and RSoXS beamline requirements: RSoXS beamlines require a light transmittance window with a thickness of 100-200 nm and a test area of ​​<1 μm to ensure soft X-ray transmittance of 240-700 eV. However, in existing devices, CN119290987A uses polyimide or quartz windows with a thickness of no less than 500 nm, and the thickness of the test structure is not under ultra-thin control; CN208818663U uses Kapton tape to seal the light transmittance hole, which has a significantly higher absorption coefficient for soft X-rays than silicon nitride, resulting in a reduced signal-to-noise ratio of the scattered signal; the thickness of the first and second windows of CN223597566U is not suitable for soft X-ray transmittance, and none of them can meet the light transmittance requirements of RSoXS beamlines. 2. In-situ testing requires the simultaneous acquisition of voltage, current, temperature, and microstructure data to establish multi-physics correlations. However, CN119290987A and CN208818663U only integrate electrochemical parameter monitoring functions and lack a temperature acquisition module. Although CN120722015A achieves wide-temperature range control through the Peltier effect, its thermocouple leads and light-transmitting window exhibit spatial interference, easily obstructing the soft X-ray path. CN110412013A and CN223597566U lack temperature monitoring design, and none of them can achieve coordinated characterization of "electro-thermal-structure". There is a deviation between the set temperature and the actual temperature in the RSoXS vacuum environment. 3. Lack of dedicated compatibility with RSoXS beamlines: RSoXS beamlines require a device compatible with a 1×0.65×0.7m³ vacuum chamber and an automated sample stage (X / Y / Z axis movement range 150-200mm, projection angle 360°). However, CN119290987A and CN208818663U use a bolted split structure, and the sealing materials (fluorine gaskets, Kapton tape) are prone to releasing gas in a high vacuum environment, contaminating the test chamber. The sealed box shape of CN110412013A is not adapted to the movement range of the sample stage, resulting in the sample not being able to accurately align with the incident light. Furthermore, none of the existing devices have optimized anti-interference structures for the K-side energy of light elements such as C, N, and O, thus failing to leverage the element resolution advantage of RSoXS. 4. Poor structural stability and test repeatability: Long-term RSoXS testing requires a stable test interface and a temperature-resistant sealing structure. However, the test interfaces of CN119290987A and CN110412013A are simple stacks, without forming a stable contact layer of less than 1μm. A thickness greater than 1μm will block the transmission of X-rays. Soft X-rays have high requirements for sample thickness. If the sample is too thick, the detector will not receive the scattered signal. In addition, it will easily cause interface separation during the charging and discharging process. The rubber sealing ring of CN120722015A and the Kapton tape of CN208818663U cannot withstand the temperature range of RSoXS beamlines from -100℃ to 300℃. Long-term testing is prone to seal failure, resulting in test interruption or non-repeatable results. Summary of the Invention

[0003] The purpose of this invention is to provide an all-solid-state battery in-situ cell adapted to synchrotron radiation resonant soft X-ray scattering beamlines, in order to solve the problems in the prior art.

[0004] The objective of this invention can be achieved through the following technical solutions: An in-situ all-solid-state battery cell adapted to a synchrotron radiation resonance soft X-ray scattering beamline is characterized by comprising: an in-situ cell body, which is composed of an upper cell body, a lower cell body, and a middle cell body, wherein the upper and lower cell bodies share a first light-transmitting hole; a battery housing mechanism, which includes a receiving groove in the middle of the middle cell body, wherein a battery assembly is disposed within the receiving groove; an electrical connection mechanism, which includes a positive electrode conductive post embedded in the upper cell body and a negative electrode conductive post embedded in the lower cell body; and a temperature monitoring mechanism, which includes mounting grooves simultaneously formed on opposite sides of the middle and lower cell bodies, wherein a thermocouple is installed within the mounting grooves.

[0005] Preferably, the battery assembly includes a battery body, with silicon substrates fixedly connected to both the upper and lower surfaces of the battery body. Each silicon substrate has a silicon nitride window in the middle. A second light-transmitting hole is opened in the middle of the battery body. An electrolyte spin coating is provided on the inner side of the middle of the second light-transmitting hole. A lithium foil layer is provided at the bottom of the second light-transmitting hole.

[0006] Preferably, the two first light-transmitting holes, the silicon nitride window, and the second light-transmitting hole are all coaxially arranged to ensure light transmittance; The first light-transmitting hole has a conical top and a rectangular bottom, and it is fitted with the upper silicon substrate. The second light-transmitting hole has a rectangular bottom and it is fitted with the lower silicon substrate.

[0007] Preferably, the upper pool body, lower pool body and middle pool body are provided with multiple sets of mounting holes, and each set of mounting holes is provided with a flat-head screw, and each flat-head screw is provided with a matching screw washer.

[0008] Preferably, the thermocouple is embedded in the pool body using a flattened solder joint structure, and the thermocouple leads are led out from the side of the lower pool body to avoid blocking the light-transmitting area.

[0009] Preferably, the lithium foil layer has a thickness of 5–20 μm and is used as a negative electrode.

[0010] Preferably, the thickness of the electrolyte spin coating is 0.5 μm.

[0011] Preferably, the lower pool body is made of thermally conductive copper, and the upper and middle pool bodies are made of stainless steel.

[0012] The beneficial effects of this invention are: 1. The 100nm silicon nitride window has excellent light transmittance, which is compatible with the ultra-thin battery structure and meets the RSoXS soft X-ray penetration requirements.

[0013] 2. It enables simultaneous acquisition of multiple parameters, including voltage, current, temperature, and scattering signals, allowing for the acquisition of various key battery information at the same time. This avoids the time lag associated with step-by-step acquisition, improves data integrity and consistency, and significantly enhances the efficiency and accuracy of battery research.

[0014] 3. The compact structure and use of non-gas-releasing materials enable it to operate stably in various complex experimental environments, accommodating vacuum and motion compatibility and adapting to the movement range of the beamline sample stage.

[0015] 4. Free from heavy metal interference, it provides pure light element signals and is suitable for K-edge analysis of light elements such as C, N, O, and F.

[0016] 5. The metal seal and copper heat-conducting block design ensure the stability and reliability of the equipment structure. This effectively prevents external interference and overheating, ensuring stable performance during long-term testing and providing solid support for continuous scientific research. Attached Figure Description

[0017] The invention will now be further described with reference to the accompanying drawings.

[0018] Figure 1 This is a schematic diagram of the all-solid-state battery in-situ cell adapted to the synchrotron radiation resonance soft X-ray scattering beamline of the present invention. Figure 2 yes Figure 1 Exploded view; Figure 3 yes Figure 2 A bottom view; Figure 4 This is an exploded view of the battery assembly; Figure 5 It is a cross-sectional plan view of the battery body; Figure 6 This is a schematic diagram of the installation of the device on the heating platform of the RSoXS synchrotron radiation beamline.

[0019] Explanation of reference numerals in the attached drawings: 1 Upper cell body, 2 Lower cell body, 3 Middle cell body, 4 Screw washer, 5 Flathead screw, 6 First light-transmitting hole, 7 Positive conductive post, 8 Negative conductive post, 9 Receiving slot, 10 Mounting slot, 11 Thermocouple, 12 Mounting hole, 13 Battery body, 14 Silicon substrate, 15 Silicon nitride window, 16 Second light-transmitting hole, 17 Electrolyte spin coating, 18 Lithium foil layer. Detailed Implementation

[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Reference Figures 1-6The all-solid-state battery in-situ cell, adapted to synchrotron radiation resonance soft X-ray scattering beamlines, includes an in-situ cell body, which is composed of an upper cell body 1, a lower cell body 2, and a middle cell body 3. The upper cell body 1 and the lower cell body 2 are provided with a first light-transmitting hole 6. The upper cell body 1, the lower cell body 2, and the middle cell body 3 are provided with multiple sets of mounting holes 12. Each set of mounting holes 12 is provided with a flat-head screw 5. Each flat-head screw 5 is provided with a matching screw washer 4. The screw washer 4 is made of PEEK material. PEEK material is high temperature resistant and has good insulation properties, which can enhance the sealing effect and avoid conductive interference. The torque is controlled at 0.5-1 N·m during assembly to ensure that the component is firmly fixed and undamaged.

[0022] This also includes a battery housing mechanism, comprising a receiving groove 9 located in the middle of the central tank 3. The receiving groove 9 is a recess with a diameter of 20.2 mm and a depth of 3.2 mm, adapted for the installation of CR2032 button batteries. A battery assembly is housed within the receiving groove 9. The battery body 13 is a CR2032 type perforated button battery, and its upper and lower surfaces are fixedly connected to silicon substrates 14 using 3M epoxy resin AB glue. During bonding, the gap must be less than 0.1 mm to enhance sealing and optical path alignment accuracy. Each silicon substrate... The dimensions of 14 are 5×5mm² and 0.5mm thick. Each of the 14 has a 1.5×1.5mm² silicon nitride window 15 with a thickness of 100nm. The battery body 13 has a second light-transmitting hole 16 in the middle. An electrolyte spin coating 17 with a thickness of 0.5μm is provided on the inner side of the middle of the second light-transmitting hole 16 to ensure ion conduction and X-ray transmittance. A lithium foil layer 18 is provided at the bottom of the second light-transmitting hole 16. The lithium foil layer 18 is a high-purity lithium foil with a purity of ≥99.9% and a thickness of 5–20μm, which is used as the negative electrode. Furthermore, this structure ensures high transmittance of K-side signals for light elements such as C, N, O, and F. The processing sequence of the battery body 13 is as follows: perforated positive electrode shell - perforated positive electrode sheet - perforated electrolyte layer - spin-coated electrolyte layer 17 - lithium foil layer 18 - perforated negative electrode shell.

[0023] (Measurement of the F-side can be achieved at 20μm, measurement of the O and F-sides can be achieved at 5μm, and measurement of the C, N, O, and F-sides can be achieved below 2μm. The above treatment of the battery body 13 ensures effective penetration of soft X-rays and in-situ observation of the SEI interface of the solid-state battery).

[0024] The two first light-transmitting holes 6, the silicon nitride window 15, and the second light-transmitting hole 16 are all coaxially arranged to ensure light transmission. The first light-transmitting hole 6 is matched with the upper silicon substrate 14, and the second light-transmitting hole 16 is a rectangular opening that is matched with the lower silicon substrate 14.

[0025] It also includes an electrical connection mechanism, which includes a positive conductive post 7 embedded inside the upper pool body 1 and a negative conductive post 8 embedded inside the lower pool body 2. The conductive post is made of brass (gold-plated to reduce contact resistance), and the outer insulating material is alumina ceramic with an insulation resistance ≥10¹²Ω to avoid leakage interference.

[0026] It also includes a temperature monitoring mechanism, which includes a mounting groove 10 with the middle pool 3 and the lower pool 2 facing each other. A thermocouple 11 is installed inside the mounting groove 10. The thermocouple 11 is embedded in the pool body with a flattened weld point structure. The temperature measurement range is -100℃ to 300℃, the resolution is 0.01℃, the temperature measurement rate is 1 time / second, and it is wirelessly connected to a handheld thermometer to transmit data in real time. The lead wire of the thermocouple 11 is led out from the side of the lower pool 2 to avoid blocking the light-transmitting area.

[0027] The upper pool 1 and the middle pool 3 are made of 304 stainless steel, and the lower pool 2 is made of T2 copper (thermal conductivity ≥380W / (m・K)) to ensure uniform heat conduction. In addition, after installation, the gaps caused by the bonding of silicon nitride windows are filled with thermally conductive copper blocks to avoid poor heat conduction in the vacuum environment. It is important to note that all sealing interfaces use metal gaskets to prevent polymer material release from contaminating the vacuum chamber and interfering with sample testing. The device size is adapted to the motion range of the synchrotron radiation sample stage (150-200mm X / Y / Z axes, 360° projection angle), and the light-transmitting window is precisely aligned with the optical path of the sample stage.

[0028] The working principle of this invention is as follows: The device is as follows Figure 6 As shown, the two first light-transmitting holes 6, the silicon nitride window 15, and the second light-transmitting hole 16 are coaxially arranged on the heating platform of the RSoXS synchrotron radiation beamline. The first light-transmitting hole 6 is matched with the upper silicon substrate 14, and the second light-transmitting hole 16 (rectangular opening) is matched with the lower silicon substrate 14 to ensure light transmission. The positive and negative terminals of the battery are connected through the positive conductive post 7 and the negative conductive post 8, respectively, to realize the connection between the battery and the external circuit for current and voltage detection. Thermocouple 11 monitors the internal temperature of the in-situ pool in real time. The data transmission wire is connected to an external handheld thermometer through the flange of the station cavity to transmit data in real time, so that operators can keep track of the internal temperature changes of the in-situ pool at any time. Synchrotron radiation resonant soft X-rays penetrate the all-solid-state battery through the first transparent aperture 6, the silicon nitride window 15, and the second transparent aperture 16. This structure ensures high transmittance of the K-side signals of light elements such as C, N, O, and F. Depending on the different thicknesses of the lithium foil layer 18, measurements of the edges of different elements can be achieved. For example, 20 μm can achieve measurements of the F-side, 5 μm can achieve measurements of the O and F-sides, and less than 2 μm can achieve measurements of the C, N, O, and F-sides. The above settings ensure effective penetration of soft X-rays and in-situ observation of the SEI interface of the solid-state battery.

[0029] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. An in-situ all-solid-state battery cell adapted to synchrotron radiation resonant soft X-ray scattering beamlines, characterized in that, include: The in-situ pool body is composed of an upper pool body (1), a lower pool body (2) and a middle pool body (3). The upper pool body (1) and the lower pool body (2) are provided with a first light-transmitting hole (6). A battery housing mechanism, the battery housing mechanism including a housing through groove (9) opened in the middle of the central pool body (3), and a battery assembly is disposed in the housing through groove (9); An electrical connection mechanism, the electrical connection mechanism including a positive electrode conductive post (7) embedded inside the upper pool body (1), and a negative electrode conductive post (8) embedded inside the lower pool body (2). The temperature monitoring mechanism includes an installation groove (10) with the middle pool (3) and the lower pool (2) facing each other, and a thermocouple (11) is installed inside the installation groove (10).

2. The all-solid-state battery in-situ cell adapted to synchrotron radiation resonant soft X-ray scattering beamlines according to claim 1, characterized in that, The battery assembly includes a battery body (13), and silicon substrates (14) are fixedly connected to the upper and lower surfaces of the battery body (13). Each silicon substrate (14) has a silicon nitride window (15) in the middle. A second light-transmitting hole (16) is opened in the middle of the battery body (13). An electrolyte spin coating layer (17) is provided on the inner side of the middle of the second light-transmitting hole (16). A lithium foil layer (18) is provided at the bottom of the second light-transmitting hole (16).

3. The all-solid-state battery in-situ cell adapted to a synchrotron radiation resonant soft X-ray scattering beamline according to claim 1, characterized in that, The two first light-transmitting holes (6), the silicon nitride window (15), and the second light-transmitting hole (16) are all coaxially arranged to ensure the light transmittance; The first light-transmitting hole (6) has a conical hole at the top and a rectangular opening at the bottom. The first light-transmitting hole (6) is matched with the upper silicon substrate (14). The second light-transmitting hole (16) has a rectangular opening and is matched with the lower silicon substrate (14).

4. The all-solid-state battery in-situ cell adapted to a synchrotron radiation resonant soft X-ray scattering beamline according to claim 1, characterized in that, The upper pool body (1), lower pool body (2) and middle pool body (3) are provided with multiple sets of mounting holes (12), and each set of mounting holes (12) is provided with a flat-head screw (5), and each flat-head screw (5) is provided with a matching screw washer (4).

5. The all-solid-state battery in-situ cell adapted to a synchrotron radiation resonant soft X-ray scattering beamline according to claim 1, characterized in that, The thermocouple (11) is embedded in the pool body using a flattened solder joint structure. The lead wire of the thermocouple (11) is led out from the side of the lower pool body (2) to avoid blocking the light-transmitting area.

6. The all-solid-state battery in-situ cell adapted to a synchrotron radiation resonant soft X-ray scattering beamline according to claim 2, characterized in that, The lithium foil layer (18) has a thickness of 5–20 μm and is used as a negative electrode.

7. The all-solid-state battery in-situ cell adapted to a synchrotron radiation resonant soft X-ray scattering beamline according to claim 2, characterized in that, The thickness of the electrolyte spin coating (17) is 0.5 μm.

8. The all-solid-state battery in-situ cell adapted to a synchrotron radiation resonant soft X-ray scattering beamline according to claim 6, characterized in that, The lower pool body (2) is made of thermally conductive copper, while the upper pool body (1) and the middle pool body (3) are made of stainless steel.

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