Sample clamping device for all-solid-state lithium battery in-situ photoelectron spectroscopy test

Abstract

The invention belongs to the field of X-ray technology application, and particularly relates to an in-situ photoelectron spectroscopy test sample clamping device for an all-solid-state lithium battery. Comprising a supporting unit with two through ends; the lower electrode is fixedly mounted at one end of the supporting unit; the upper electrode is fixedly mounted at the other end of the supporting unit, allows the X-rays to pass through and is used for being matched with the lower electrode to provide an electric field for the all-solid-state battery; the sample table is located in a cavity defined by the supporting unit, the lower electrode and the upper electrode and used for clamping the all-solid-state battery between the lower electrode and the upper electrode to form a closed loop. The device can perform continuous testing on the same sample, can monitor the dynamic change of the battery in the charging and discharging process in real time, and is beneficial to capturing the instantaneous interface reaction and structure evolution, so that the working mechanism and the interface evolution process of the all-solid-state lithium battery can be researched more comprehensively and accurately.

Description

Technical Field

[0001] The invention belongs to the field of X-ray technology application, and in particular relates to a sample clamping device for in-situ photoelectron energy spectrum testing of all-solid-state lithium batteries. Background Art

[0002] All-solid-state batteries with high energy density and high stability are considered to be one of the most promising next-generation energy storage devices and have been widely studied in industries such as mobile electronic devices and electric vehicles. However, the development of high-performance all-solid-state batteries requires a systematic and in-depth understanding of the dynamic evolution of the microstructure, phase composition, chemical composition, local chemical environment, etc. inside and at the interface of the battery. Among them, the formation of a solid electrolyte interface film (SEI layer) with ion conduction and electronic insulation properties is the key to the stable operation of the battery. Monitoring the evolution of the solid electrolyte interface film is crucial to optimizing the stable service characteristics of all-solid-state lithium-ion batteries.

[0003] The activity of lithium metal and the buried solid-solid interface pose challenges to the dynamic monitoring of in-situ lithium deposition and chemical evolution of solid electrolyte interface films. Due to its surface and interface sensitive characteristics, photoelectron spectroscopy technology has been applied to the study of atomic and electronic structures such as elemental composition and coordination environment of the SEI layer. However, most of the current photoelectron spectroscopy tests on all-solid-state lithium batteries are carried out in a non-in-situ state, that is, different samples, different environments, and different states: multiple samples need to be prepared, and charge and discharge tests are carried out at different current densities for different times, and then they are taken out of their working environment and transferred to the test cavity. In this case, slight differences in the preparation process of multiple samples and chemical reactions such as surface oxidation that may occur during sample transfer will cause the analysis results to fail to reflect the true working state of the battery.

[0004] In summary, the existing non-in-situ testing has the following problems: 1. Minor differences in sample preparation may lead to inconsistent test results; 2. Chemical reactions such as surface oxidation may occur during sample transfer, affecting the accuracy of the test results; 3. It is impossible to monitor the interface evolution process of the battery in real time when it is working.

[0005] Therefore, it is of great significance to develop a sample clamping device that can simulate the real working environment of the battery and realize in-situ dynamic monitoring. Summary of the invention

[0006] The purpose of the present invention is to provide a sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries, which can simulate the real working environment of the battery and realize dynamic monitoring of lithium plating / stripping and SEI layer of the same battery under different conditions.

[0007] To achieve the above object, the present invention provides a sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries, comprising: A support unit, wherein both ends of the support unit are connected; A lower electrode, the lower electrode being fixedly mounted at one end of the supporting unit; An upper electrode, which is fixedly mounted at the other end of the support unit and allows X-rays to pass through, and is used to cooperate with the lower electrode to provide an electric field for the all-solid-state battery; A sample stage is located in a cavity surrounded by the support unit, the lower electrode and the upper electrode, and is used to clamp the all-solid-state battery between the lower electrode and the upper electrode to form a closed loop.

[0008] Preferably, the support unit is insulated as a whole, and comprises a first support body and a second support body; One end of the first support body is coaxially mounted inside the second support body, and the other end is fixedly mounted on the lower electrode; An upper electrode is fixedly mounted on one end of the second support body away from the first support body.

[0009] Preferably, corresponding threaded holes are provided at one end of the first supporting body and the second supporting body that are connected to each other; An insulating bolt is inserted into the threaded hole to fix the first support body and the second support body together.

[0010] Preferably, the upper electrode comprises a pressure ring, a gold mesh and a pressure sheet which are stacked in sequence; The pressing ring overlaps with the edge of the gold mesh and fixes the gold mesh on a side of the pressing sheet close to the supporting unit; The pressing sheet is fixedly mounted at one end of the supporting unit and is provided with an opening in the middle for the passage of X-rays; The opening is completely covered by the gold mesh.

[0011] Preferably, the gold mesh is a mesh structure made of single-element gold.

[0012] Preferably, the sample stage comprises: A positioning column, one end of which is mounted on the lower electrode, and the other end of which is expanded to form a limiting ring; A support platform, the support platform is fixedly installed above the limiting ring and is used to carry the all-solid-state battery; A spring is sleeved on the outer circumference of the positioning column, and two ends of the spring are respectively in contact with the limiting ring and the lower electrode.

[0013] Preferably, the positioning column is fixed to the lower electrode by threaded engagement; The thickness of the lower electrode at the threaded engagement portion corresponding to the positioning column is increased.

[0014] Preferably, a plurality of threaded holes are formed along a height direction at one end of the first support body close to the second support body.

[0015] Preferably, an insulating layer is provided on a side of the lower electrode away from the supporting unit, for isolating the lower electrode from the standard sample holding system, so that the lower electrode is isolated from the ground wire; The standard sample holding system is a commercial or laboratory photoelectron spectroscopy sample holding system.

[0016] Preferably, the pressing tablet is connected to a standard sample holding system via a wire; The standard sample holding system is connected to an electrochemical workstation or a constant potential instrument via a wire.

[0017] The beneficial effects of the present invention are: 1. Support in-situ testing: The present invention can simulate the real working environment of the battery, realize the dynamic monitoring of lithium plating / stripping and SEI layer of the same battery under different conditions, and avoid errors in sample preparation and transfer in non-in-situ testing.

[0018] 2. Wide range of battery sizes: The present invention can change the distance between the upper electrode and the support platform by changing the depth of the threaded connection between the positioning column and the lower electrode or by matching the threaded holes on the second support body with threaded holes at different heights on the first support body. This can adapt to the clamping needs of all-solid-state lithium batteries of different thicknesses, making the application range of the present invention wider. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a schematic diagram of the internal structure of the clamping device of the present invention; Figure 2 This is a schematic diagram of disassembly and assembly of the clamping device of the present invention; In the figure: 1. insulating layer; 2. lower electrode; 3. sample stage; 301. spring; 302. positioning column; 303. support platform; 4. support unit; 401. first support body; 402. second support body; 5. all-solid-state battery; 6. upper electrode; 601. pressure ring; 602. gold mesh; 603. pressing sheet. DETAILED DESCRIPTION

[0020] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0021] like Figure 1 to Figure 2As shown, the present invention provides a sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries, comprising: a support unit 4, wherein both ends of the support unit 4 are connected; a lower electrode 2, wherein the lower electrode 2 is fixedly mounted at one end of the support unit 4; an upper electrode 6, wherein the upper electrode 6 is fixedly mounted at the other end of the support unit 4 and allows X-rays to pass through, and is used to cooperate with the lower electrode 2 to provide an electric field for an all-solid-state battery 5; and a sample stage 3, wherein the sample stage 3 is located in a cavity surrounded by the support unit 4, the lower electrode 2 and the upper electrode 6, and is used to clamp the all-solid-state battery 5 between the lower electrode 2 and the upper electrode 6 to form a closed loop.

[0022] The support unit 4 is an overall frame, made of insulating material, and the through-hole design at both ends facilitates the installation of other components such as the upper electrode 6 and the lower electrode 2. The lower electrode 2 is fixedly mounted on one end of the support unit 4 and is made of a conductive metal material, such as stainless steel, tantalum, or platinum, and is used to contact one side of the all-solid-state battery 5 and provide an electric field. The upper electrode 6 is fixedly mounted on the other end of the support unit 4, and is also made of a conductive metal material, but its structural design allows X-rays to pass through, for example, a metal ring or metal mesh structure with a center hole can be used. The upper electrode 6 cooperates with the lower electrode 2 to provide an electric field for the all-solid-state battery 5, simulating the actual working environment of the battery. The sample stage 3 is located in the cavity surrounded by the support unit 4, the lower electrode 2 and the upper electrode 6, and is used to clamp the all-solid-state battery 5 between the lower electrode 2 and the upper electrode 6 to form a closed loop.

[0023] In actual operation, the all-solid-state battery 5 sample is first placed on the sample stage 3, and then the height of the sample stage 3 is adjusted to make the battery sample in close contact with the upper electrode 6 and the lower electrode 2. The upper electrode 6 and the lower electrode 2 are connected to an external power supply to provide the necessary electric field. When X-rays are irradiated to the surface of the battery sample through the openings or grid structure of the upper electrode 6, the generated photoelectrons can be detected by the photoelectron spectrometer through the same path.

[0024] This allows the battery to be directly subjected to photoelectron spectroscopy analysis while in working condition, avoiding chemical reactions such as surface oxidation that may occur during sample transfer, and ensuring that the test results truly reflect the working condition of the battery.

[0025] Optionally, the support unit 4 is insulated as a whole, and includes a first support body 401 and a second support body 402; one end of the first support body 401 is coaxially mounted inside the second support body 402, and the other end is fixedly mounted on the lower electrode 2; the upper electrode 6 is fixedly mounted on one end of the second support body 402 away from the first support body 401.

[0026] Specifically, one of the insulating materials such as polyetheretherketone, ceramic or polytetrafluoroethylene is used to make the first support body 401 and the second support body 402 so that the entire support unit 4 is insulated, and the upper electrode 6, the lower electrode 2 and the support platform 303 are electrically isolated to prevent short circuit or leakage caused by direct contact, and to ensure the electrochemical stability of the test system. The all-solid-state battery 5 is placed on the sample table 3 inside the support unit 4. The overall insulated support unit 4 ensures the purity of its internal test environment and avoids external electric field interference, thereby improving the accuracy of the test results. Optionally, the size and shape of the docking part of the first support body 401 and the second support body 402 can be adapted, and then the coaxial installation can be automatically achieved when the first support body 401 is inserted into the second support body 402. Of course, the coaxial installation of the first support body 401 and the second support body 402 can also be achieved by the cooperation of the protrusion or the slide groove or by using the guide pin.

[0027] The coaxially mounted first support body 401 and second support body 402 can achieve accurate alignment of the upper electrode 6 and the lower electrode 2, ensuring uniform force on the all-solid-state battery 5 and ensuring test accuracy.

[0028] Optionally, corresponding threaded holes are provided at one end of the first support body 401 and the second support body 402 that are connected to each other; insulating bolts are inserted into the threaded holes to fix the first support body 401 and the second support body 402 together.

[0029] Specifically, the first support body 401 and the second support body 402 can be firmly fixed together by this threaded connection. When disassembly or adjustment is required, it is only necessary to loosen the insulating bolts. For example, when placing the all-solid-state battery 5 on the sample stage 3, the second support body 402 can be removed, so that the upper end of the first support body 401 is open, which is convenient for placing the all-solid-state battery 5.

[0030] Furthermore, the insulating bolt can be made of an insulating material such as polyetheretherketone, ceramic or polytetrafluoroethylene.

[0031] Compared with the traditional welding or bonding methods, the method of fixing with insulating bolts has many advantages: First, it can provide a reliable mechanical connection. The threaded connection can withstand large axial forces and torques, ensuring the stability of the support unit 4 during use.

[0032] Second, the insulating bolt itself is not conductive, and it can connect the first support body 401 and the second support body 402 while ensuring electrical isolation, thereby preventing current leakage and interference during the test process and helping to improve the accuracy of the test results.

[0033] Third, the combined height between the first support body 401 and the second support body 402 can be adjusted. Optionally, a plurality of threaded holes are provided along the height direction at one end of the first support body 401 close to the second support body 402. By aligning the threaded holes on the second support body 402 with threaded holes at different heights on the first support body 401 and then inserting insulating bolts to fix them, the height of the second support body 402 relative to the first support body 401 can be adjusted to adapt to all-solid-state batteries 5 of different thicknesses or testing requirements.

[0034] Optionally, the upper electrode 6 includes a pressure ring 601, a gold mesh 602 and a pressing plate 603 which are stacked in sequence; the pressure ring 601 overlaps with the edge of the gold mesh 602 and fixes the gold mesh 602 on the side of the pressing plate 603 close to the support unit 4; the pressing plate 603 is fixedly installed at one end of the support unit 4 and an opening is provided in the middle for the passage of X-rays; the opening is completely covered by the gold mesh 602.

[0035] Specifically, the pressing sheet 603, as the main structure of the upper electrode 6, is fixedly mounted at one end of the supporting unit 4, and is provided with an opening in the middle to allow X-rays to pass through. This opening is the key to achieving X-rays passing through the upper electrode 6. The size of the opening can be adjusted according to actual needs, for example, it can be set to a circular opening with a diameter of 1-5 mm to adapt to different X-ray beam sizes and test requirements.

[0036] The gold mesh 602 covers the opening of the pressing sheet 603 and completely covers the opening. The function of the gold mesh 602 is to maintain the conductivity and uniformity of the electrode while allowing the X-ray to pass through, thereby ensuring the stability of the electric field.

[0037] The gold mesh 602 can be selected with different mesh densities, such as 50-200 lines per inch, and the specific model can be selected (Manufacturer-Precisioneforming / Model-MG49 117.6LPI Au Mesh 11”x11”) to achieve a balance between X-ray transmittance and conductivity. The thickness of the gold mesh 602 can be selected between 10-100μm, which must ensure sufficient mechanical strength but not be too thick to affect X-ray transmission.

[0038] The edge of the pressure ring 601 overlaps with the gold mesh 602, and the gold mesh 602 is fixedly clamped on the side of the pressing sheet 603 close to the supporting unit 4, ensuring the stability and reliability of the gold mesh 602 and preventing displacement or deformation during the test.

[0039] The pressure ring 601 can be made of the same material as the insulating bolt, such as polyetheretherketone, ceramic or polytetrafluoroethylene. The pressure plate 603 can be fixed to the second support body 402 by bolts, and its material can be one of the metal materials such as stainless steel, tantalum or platinum to ensure good conductivity and corrosion resistance. The thickness of the pressure ring 601 can be designed to be 0.5-2mm to provide sufficient pressure to fix the gold mesh 602.

[0040] The combined design of these three components solves the problem that traditional solid electrodes cannot meet the X-ray penetration requirements, while also avoiding the problems of insufficient mechanical strength and deformation that may be caused by simply using gold mesh 602 as an electrode.

[0041] Furthermore, the gold mesh 602 can be a mesh structure made of elemental gold. Because gold has good electrical conductivity and chemical stability, and absorbs less X-rays. The mesh structure of the gold mesh 602 can be further optimized, for example, by using a honeycomb or regular hexagonal mesh to maximize the X-ray transmittance while ensuring strength. Thus, the structural design of the upper electrode 6 of the present application achieves an organic combination of electrical conductivity, X-ray transmittance and structural stability, providing reliable technical support for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries.

[0042] Optionally, the sample stage 3 includes: a positioning column 302, one end of which is installed on the lower electrode 2, and the other end is enlarged to form a limiting ring; a support platform 303, the support platform 303 is fixedly installed above the limiting ring and is used to support the all-solid-state battery 5; a spring 301, the spring 301 is sleeved on the outer periphery of the positioning column 302, and the two ends of the spring 301 are respectively in contact with the limiting ring and the lower electrode 2.

[0043] Specifically, the diameter of the limiting ring can be designed according to actual needs, and is usually 20% to 50% larger than the diameter of the positioning column 302, so that the spring 301 has enough force application space. The support table 303 is fixedly installed above the limiting ring and directly supports the all-solid-state battery 5. The material of the support table 303 can be selected from metals with good conductivity and corrosion resistance, such as stainless steel or copper alloy. The surface of the support table 303 can be polished to ensure good contact with the battery.

[0044] The spring 301 is sleeved on the outer periphery of the positioning column 302, and its two ends are respectively in contact with the limit ring and the lower electrode 2. The material of the spring 301 can be an alloy with good elasticity and corrosion resistance, such as stainless steel or copper. The spring 301 allows the support table 303 to move flexibly in the vertical direction through its elastic deformation characteristics, so as to adapt to all-solid-state battery 5 samples of different thicknesses. In an ultra-high vacuum or dynamic testing environment, the elasticity of the spring 301 can continuously provide contact pressure to offset the slight displacement of the positioning column 302 caused by thermal expansion, mechanical vibration or sample deformation, thereby ensuring the tightness of the connection between the positioning column 302 and the lower electrode 2 and avoiding electrical connection interruption.

[0045] Furthermore, the positioning column 302 can be fixed to the lower electrode 2 by means of a threaded connection, so that the distance between the support platform 303 and the upper electrode 6 can be adjusted by pre-adjusting the threaded engagement depth of the positioning column 302 on the lower electrode 2 to meet the clamping requirements of all-solid-state battery 5 samples of different thicknesses. Thus, together with the method of adjusting the combined height of the first support body 401 and the second support body 402 to meet the clamping requirements of all-solid-state battery 5 samples of different thicknesses, two different adjustment methods of coarse and fine adjustment precisions are formed, which expands the clamping adaptation space of the clamping device.

[0046] Among them, when there are multiple positioning columns 302, the support platform 303 can be fixedly installed above the limiting ring by means of a threaded connection, so that when the positioning column 302 needs to be rotated, the support platform 303 can be removed from the limiting ring to avoid multiple positioning columns 302 being locked by the support platform 303 at the same time and unable to rotate.

[0047] Furthermore, the thickness of the threaded engagement portion of the lower electrode 2 corresponding to the positioning post 302 can be appropriately increased so that the positioning post 302 can obtain more thread screwing space on the lower electrode 2 to expand the height adjustment range of the positioning post 302 .

[0048] Optionally, an insulating layer 1 is provided on the side of the lower electrode 2 away from the supporting unit 4, which is used to isolate the lower electrode 2 from the standard sample supporting system, so that the lower electrode 2 is isolated from the ground wire; the standard sample supporting system is a commercial or laboratory photoelectron energy spectrum sample supporting system.

[0049] Specifically, the insulating layer 1 can be implemented in a variety of materials and forms, for example, a film or coating made of ceramic, polymer or other insulating materials can be used. The thickness of the insulating layer 1 can be adjusted according to actual needs, usually between 0.1 mm and 2 mm. The insulating layer 1 can be fixed to the side of the lower electrode 2 away from the support unit 4 by bonding, hot pressing or other appropriate methods.

[0050] The provision of the insulating layer 1 realizes the isolation of the lower electrode 2 from the ground line, and can more accurately control the distribution of the electric field, thereby improving the accuracy of the test. In addition, the presence of the insulating layer 1 can also prevent unnecessary electron transmission that may occur between the lower electrode 2 and the standard sample holding system, further ensuring the reliability of the test results.

[0051] Preferably, the insulating layer 1 can be made of ceramic material with a thickness of 0.5 mm. This material has excellent insulation performance and heat resistance and can remain stable in a high temperature environment. The insulating layer 1 is fixed to the side of the lower electrode 2 away from the support unit 4. The lower electrode 2 can be made of stainless steel. The standard sample holding system can use the commercial PTS sample holding system of the Polish Prevac brand, the model is a standard resistance sample holder.

[0052] In this embodiment, the insulating layer 1 completely covers the contact surface between the lower electrode 2 and the standard sample holding system, effectively preventing any possible electron transmission. At the same time, since the insulating layer 1 is relatively thin, it will not significantly affect the overall size and structure of the sample holding device. The standard sample holding system is connected to the photoelectron spectrometer through a dedicated interface to ensure stable signal transmission. Researchers can directly install the sample holding device on the existing photoelectron spectrometer without major modifications to the instrument, thereby greatly reducing the implementation cost and difficulty.

[0053] Optionally, the pressing sheet 603 is connected to a standard sample holding system via a wire; the standard sample holding system is connected to an electrochemical workstation or a constant potential instrument via a wire.

[0054] Specifically, the standard sample holding system uses a commercial photoelectron spectroscopy sample holding system with multiple electrical interfaces. One interface is connected to the pressing sheet 603 through a wire, and the other interface is connected to the electrochemical workstation through a shielded cable. The electrochemical workstation can use the electrochemical workstation model CHI760E produced by Shanghai Chenhua Instrument Co., Ltd. The control software of the electrochemical workstation can set different charge and discharge parameters, such as constant current density, cut-off voltage, etc., to change the test scenario.

[0055] In the actual test process, the all-solid-state lithium battery sample is first placed on the sample stage 3, and the sample position is adjusted so that it is in good contact with the upper and lower electrodes 2. Then the sample clamping device is installed on the standard sample holding system, and all electrical connections are completed. The entire system is placed in the ultra-high vacuum chamber of the photoelectron spectrometer and evacuated to the required pressure.

[0056] Start the electrochemical workstation and set the required charge and discharge parameters, such as constant current charging at a rate of 0.1C to 4.2 V. At the same time, start the photoelectron spectrometer, set the X-ray source parameters and energy analyzer parameters, and start collecting data.

[0057] During the charge and discharge process, the chemical composition and electronic structure changes of the all-solid-state lithium battery interface can be observed in real time. As a result, researchers can directly observe the formation and evolution of the SEI layer under the working state of the battery and obtain more real and reliable experimental data.

[0058] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries, characterized in that: include: A support unit (4), wherein both ends of the support unit (4) are connected; A lower electrode (2), wherein the lower electrode (2) is fixedly mounted on one end of the support unit (4); an upper electrode (6), the upper electrode (6) being fixedly mounted on the other end of the support unit (4) and allowing X-rays to pass through, and being used to cooperate with the lower electrode (2) to provide an electric field for the all-solid-state battery (5); A sample stage (3), the sample stage (3) being located in a cavity surrounded by the support unit (4), the lower electrode (2) and the upper electrode (6), and being used for clamping the all-solid-state battery (5) between the lower electrode (2) and the upper electrode (6) to form a closed loop.

2. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 1, characterized in that: The support unit (4) is insulated as a whole, and comprises a first support body (401) and a second support body (402); One end of the first support body (401) is coaxially mounted inside the second support body (402), and the other end is fixedly mounted on the lower electrode (2); An upper electrode (6) is fixedly mounted on one end of the second support body (402) away from the first support body (401).

3. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 2, characterized in that: A corresponding threaded hole is provided at one end of the first support body (401) and the second support body (402) that are connected to each other; An insulating bolt is inserted into the threaded hole and is used to fix the first support body (401) and the second support body (402) together.

4. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 1, characterized in that: The upper electrode (6) comprises a pressure ring (601), a gold mesh (602) and a pressure sheet (603) which are stacked in sequence; The pressing ring (601) overlaps with the edge of the gold mesh (602) and fixes the gold mesh (602) on a side of the pressing sheet (603) close to the support unit (4); The pressing sheet (603) is fixedly mounted on one end of the supporting unit (4) and is provided with an opening in the middle for the passage of X-rays; The opening is completely covered by the gold mesh (602).

5. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 4, characterized in that: The gold mesh (602) is a mesh structure made of single-element gold.

6. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 1, characterized in that: The sample stage (3) comprises: A positioning column (302), one end of the positioning column (302) being mounted on the lower electrode (2), and the other end being expanded to form a limiting ring; A support platform (303), the support platform (303) being fixedly mounted above the limiting ring and used for supporting the all-solid-state battery (5); A spring (301), wherein the spring (301) is sleeved on the outer circumference of the positioning column (302), and two ends of the spring (301) are respectively in contact with the limiting ring and the lower electrode (2).

7. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 6, characterized in that: The positioning column (302) is fixed to the lower electrode (2) through threaded engagement; The thickness of the threaded engagement portion of the lower electrode (2) corresponding to the positioning column (302) is increased.

8. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 1, characterized in that: A plurality of threaded holes are provided along the height direction at one end of the first support body (401) close to the second support body (402).

9. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 1, characterized in that: An insulating layer (1) is provided on a side of the lower electrode (2) away from the support unit (4), for isolating the lower electrode (2) from the standard sample supporting system, so that the lower electrode (2) is isolated from the ground wire; The standard sample holding system is a commercial or laboratory photoelectron spectroscopy sample holding system.

10. The sample clamping device for in-situ photoelectron spectroscopy testing of all-solid-state lithium batteries according to claim 4, characterized in that: The pressing sheet (603) is connected to a standard sample carrying system via a wire; The standard sample holding system is connected to an electrochemical workstation or a constant potential instrument via a wire.

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