Solid-state battery in-situ measurement device and its tabletting tool

Abstract

The utility model provides a kind of solid-state battery in-situ measuring device and its tabletting tool, the middle part of the shell of measuring device is equipped with through-hole, the rear section hole cavity of through-hole contains battery sample assembly;First electrode is inserted in through-hole, and there is second electrode on the shell of the rear end of through-hole.The middle part of the base of tabletting tool is equipped with the blind hole containing insulating ring, insulating ring is clamped between top cover and the hole bottom of blind hole, and top cover middle part is equipped with top cover hole for inserting pressing rod.The utility model mainly sets blind hole on tabletting tool, and battery sample is adhered in the ring hole bottom of insulating ring by pressing rod pressurization.When carrying out experiment, battery sample assembly is placed in the hole cavity of the through-hole of battery in-situ measuring device, and battery sample assembly is more convenient and has no risk of breakage.

Description

Technical Field

[0001] This utility model relates to the field of battery in-situ characterization and testing technology, specifically to a solid-state battery in-situ measurement device and its pressing fixture. Background Technology

[0002] In in-situ battery research, X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques can be used to measure the structural and chemical state changes of battery materials during charging and discharging in real time. The main purpose of in-situ battery measurement is to find ways to further improve battery cycle performance from the perspective of these change principles. "In-situ" measurement refers to the real-time, dynamic measurement and characterization of the materials, interfaces, reactions, or states inside the battery during its actual operation, directly under its original working state and real-world environment.

[0003] In existing technologies, in-situ measurement experiments on solid-state batteries typically involve first pressing small, round battery samples using a pellet press, and then clamping these samples inside an in-situ battery measurement device. This device includes a sample mounting stage, positive and negative electrode terminals, a mounting base, and a transmission window. The battery sample is fitted with a dedicated solid-state mold to hold the solid electrolyte, positive electrode material, and negative electrode material, and then transferred as a whole to the solid-state in-situ cell and placed on the mounting stage. Applying pressure is necessary to ensure effective and tight contact between the electrode materials; otherwise, the phase transition process and conductivity of the battery materials will be affected. Existing patents such as CN10A4393223A, KR2020110A000384U, and US9022652B2 all include components for applying pressure to the battery sample. However, the pressure applied to the battery sample using these technologies is difficult to control, and because the round battery samples are small, controlling the pressure during handling and pressurization can easily lead to breakage. Utility Model Content

[0004] The primary objective of this invention is to provide an in-situ measurement device for solid-state batteries, which facilitates the handling of battery samples and ensures the integrity of the battery samples.

[0005] Another objective of this invention is to provide a pressing fixture capable of pressing out the battery sample assembly required by the aforementioned measuring device.

[0006] To achieve the above objectives, the technical solution adopted by this utility model is as follows: a through hole is provided in the middle of the housing for X-rays to pass through from front to back. The rear section of the through hole accommodates the battery sample assembly to be tested. The battery sample assembly includes an insulating ring and a sheet-like battery sample disposed at the rear end of the central hole of the insulating ring. The through hole and the central hole of the insulating ring form a through hole extending in the front and back direction. A tubular first electrode with the core direction aligned with the core of the through hole and the central hole is inserted into the through hole from front to back. A plate-like second electrode is provided on the housing at the rear end of the through hole. A front beryllium window plate and a rear beryllium window plate are attached to the front and rear sample surfaces of the battery sample. The rear end of the first electrode abuts against the front beryllium window plate, and the front plate surface of the second electrode abuts against the rear beryllium window plate. The front end of the first electrode is exposed at the front of the housing. The second electrode has a light-passing hole corresponding to the area where the sample surface of the battery sample is located. Insulation is provided between the first electrode and the second electrode.

[0007] A pressing fixture for an in-situ measurement device for solid-state batteries includes a base with a blind hole in the middle for accommodating an insulating ring. The bottom rear end of the annular hole of the insulating ring is used to form a sheet-shaped battery sample. The top of the base has an annular top cover that is detachably connected to the base. The insulating ring is sandwiched between the top cover and the bottom of the blind hole. The top cover has a top cover hole in the middle for inserting a pressing rod. The core direction of the top cover hole is consistent with that of the annular hole. The pressing rod and the annular hole, as well as the pressing rod and the top cover hole, are clearance fits.

[0008] This invention primarily involves creating blind holes in a pressing fixture to accommodate an insulating ring and a battery sample. A pressure rod applies pressure to adhere the battery sample to the bottom of the hole in the insulating ring, thus forming a single battery sample assembly. During experiments, the battery sample assembly is placed within the cavity of the through-hole in the battery in-situ measurement device, positioning the battery sample along the X-ray penetration or diffraction path. Because the volume of the battery sample assembly, consisting of the battery sample and the insulating ring, is significantly larger than that of traditional small, disc-shaped battery samples, handling only requires holding the insulating ring without direct contact with the battery sample, making handling more convenient and eliminating the risk of breakage. Attached Figure Description

[0009] Figure 1 , 5 These are isometric views of the front and back sides of the solid-state battery in-situ measurement device, respectively.

[0010] Figure 2 , 6 They are respectively Figure 1 Cross-sectional views at LL and MPN;

[0011] Figure 3 for Figure 2 A magnified view of a section at point K;

[0012] Figure 4 for Figure 2A schematic diagram of the battery sample assembly after removing the first electrode, the front beryllium window, and the battery sample assembly;

[0013] Figure 7 This is a cross-sectional view of the battery sample assembly;

[0014] Figure 8 This is an isometric view of the tablet compression fixture;

[0015] Figure 9 This is a cross-sectional view of the tablet compression fixture;

[0016] Figure 10 for Figure 9 A magnified view of a section at point J;

[0017] Figure 11 Graph showing in-situ battery charge / discharge test.

[0018] Figure 12 This is a graph of in-situ XAFS test data. Detailed Implementation

[0019] See Figures 1-7 The solid-state battery in-situ measurement device shown has a through hole 10a in the middle of the housing 10 for X-rays to pass through from front to back. The rear cavity of the through hole 10a accommodates the battery sample assembly A20 to be tested. The battery sample assembly A20 includes an insulating ring A22 and a sheet-like battery sample A21 disposed at the rear end of the central hole A221 of the insulating ring A22.

[0020] The through hole 10a and the central hole A221 of the insulating ring A22 form a through hole extending in the front and back direction. A tubular first electrode 30 with the same core direction as the through hole 10a and the central hole A221 is inserted into the through hole from front to back. A plate-shaped second electrode 40 is provided on the housing 10 at the rear end of the through hole 10a. A front beryllium window plate 51 and a rear beryllium window plate 52 are attached to the front and rear sample surfaces of the battery sample A21. The rear end of the first electrode 30 is pressed against the front beryllium window plate 51, and the front plate surface of the second electrode 40 is pressed against the rear beryllium window plate 52. The front end of the first electrode 30 is exposed in front of the housing 10. The second electrode 40 has a light-passing hole 401 corresponding to the area where the sample surface of the battery sample A21 is located. Insulation is provided between the first electrode 30 and the second electrode 40.

[0021] In the above scheme, battery sample A21 is press-fitted together with insulating ring A22 using a pressing fixture to form battery sample assembly A20. X-rays pass through the polyimide film 60, front beryllium window 51, battery sample A21, and rear beryllium window 52 within the through-hole 10a cavity to perform transmission mode or fluorescence mode experiments. The beryllium window has conductive properties, and metallic beryllium can be passed through by X-rays. One of the first electrode 30 and the second electrode 40 is connected to the positive terminal of the power supply, and the other electrode is connected to the negative terminal of the power supply, that is, current is conducted between the first electrode 30, front beryllium window 51, battery sample A21, rear beryllium window 52, ​​and second electrode 40. Since the volume of battery sample assembly A20 is much larger than that of traditional small circular battery samples, it is only necessary to hold the insulating ring A22 when handling the sample without directly contacting the battery sample A21, making handling more convenient and eliminating the risk of breakage. The rear end of the first electrode 30 presses against the front beryllium window plate 51, and the pressure is transmitted to the battery sample A21 through the front beryllium window plate 51. The battery sample A21 is sandwiched in the middle by the front beryllium window plate 51 and the rear beryllium window plate 52, and the rear plate surface of the rear beryllium window plate 52 presses against the front plate surface of the second electrode 40. This provides a pressure environment for the battery sample A21 and ensures its conductivity under measurement conditions.

[0022] To facilitate pressurizing battery sample A21, the outer wall of the first electrode 30 inserted into the cavity of the through hole 10a forms a threaded fit with the inner wall of the through hole 10a. Rotating the outer wall of the first electrode 30 using a lead screw principle compresses the front beryllium window plate 51 to apply pressure to battery sample A21. This facilitates manual operation, and the pressure is controllable and reliable. (Instruction manual attached) Figure 11 , Figure 12 The figures show in-situ battery charge-discharge test diagrams and in-situ XAFS test data obtained using a solid-state battery in-situ measurement device.

[0023] More specifically, the housing 10 includes a front cover 11, an insulating pad 12, and a rear cover 13 stacked sequentially from front to back, with their central through holes connected to form a through hole 10a. The second electrode 40 rests against the rear plate surface of the rear cover 13, and the central part of the rear cover 13 is an enlarged section of the through hole 10a for accommodating the battery sample assembly A20 under test. The insulating pad 12 isolates the front cover 11 and the rear cover 13, preventing a short circuit between the first electrode 30 and the second electrode 40 through the housing 10. The insulating pad 12 is typically made of plastic.

[0024] Preferably, the front and rear sides of the battery sample A21 are respectively held and abutted by a front beryllium window plate 51 and a rear beryllium window plate 52. The diameter of the front beryllium window plate 51 is the same as the diameter of the tube segment into which the first electrode 30 is inserted through the through hole 10a. A sealing ring 80 is provided between the rear cover 13 and the rear beryllium window plate 52. Figure 2 , Figure 4As shown, during the experiment, the front cover 11, insulating pad 12 and rear cover 13 are first separated. Then, the battery sample assembly A20 is filled into the enlarged diameter section of the through hole 10a in the center of the rear cover 13. After that, the insulating pad 12 and the front cover 11 are installed in sequence. The front beryllium window plate 51 and the rear beryllium window plate 52 are installed in front and behind the battery sample A21, respectively. The first electrode 30 is inserted into the through hole 10a from front to back, so that the rear end of the first electrode 30 abuts against the front beryllium window plate 51. The second electrode 40 is installed on the rear plate surface of the rear cover 13 so that it is close to the rear beryllium window plate 52.

[0025] In order to seal the battery sample A21, sealing rings 80 are provided between the front cover 11 and the insulating pad 12, between the insulating pad 12 and the rear cover 13, and between the rear cover 13 and the second electrode 40 or the rear beryllium window plate 52, to ensure that the battery sample assembly A20 does not come into contact with the outside world.

[0026] A more preferred embodiment is that the front cover 11 has a recessed cavity in the middle to accommodate the fixing ring 14. The inner hole of the fixing ring 14 is threadedly engaged with the outer tube wall at the corresponding position of the first electrode 30. The outer ring wall of the fixing ring 14 and the front cover 11 have corresponding pin holes 111. The pin holes 111 on the front cover 11 penetrate the side wall of the recessed cavity and the outer wall of the front cover 11, and the core of the pin hole 111 is perpendicular to the core of the through hole 10a. A sealing ring 80 is provided between the fixing ring 14 and the insulating gasket 12. Providing the fixing ring 14 in the middle of the front cover 11 makes it easier to machine threads on the inner wall of the fixing ring 14, and inserting a pin into the pin hole 111 can limit the circumferential movement of the fixing ring 14.

[0027] Preferably, a disc-shaped pressure head 31 is provided at the suspension end of the first electrode 30 extending forward from the through hole 10a. A pressure cap 32 is provided on the front disc surface of the pressure head 31. A polyimide film 60 is sandwiched between the pressure head 31 and the pressure cap 32, and the film covers the X-ray penetration path. A stepped hole with a diameter larger than that of the through hole 10a is provided in the middle of the front end face of the pressure head 31, and the pressure cap 32 is placed at the stepped hole. The stepped hole and the through hole 10a extend sequentially through each other in the front-rear direction. The pressure head 31 allows the operator to easily rotate the first electrode 40 to apply pressure to the battery sample A21, and the pressure head 31 also provides space for mounting the polyimide film 60.

[0028] More specifically, the front cover 11, insulating pad 12, and rear cover 13 are provided with corresponding front bolt holes 121, and the rear cover 13 and the second electrode 40 are provided with corresponding rear bolt holes 131. The first electrode 30 extends forward from the suspension end of the through hole 10a, and the side plate edge of the second electrode 40 is provided with insertion holes 132 for inserting electrode rods 70. The core direction of the electrode rod 70 is perpendicular to the core of the through hole 10a. An "L"-shaped bracket 1 is connected to the side of the plate of the housing 10. In the above scheme, the bolts in the front bolt holes 121 can fix the front cover 11, insulating pad 12, and rear cover 13 together, and the bolts in the rear bolt holes 131 can fix the rear cover 13 and the second electrode 40 together. The housing 10 is fixed to the worktable by the bracket 1.

[0029] See Figures 7-10 The solid-state battery in-situ measurement device shown has a pressing fixture. The base B20 has a blind hole B40 in the middle to accommodate an insulating ring A22. The bottom rear end of the central hole A221 of the insulating ring A22 is used to form a sheet-shaped battery sample A21. The top of the base B20 has an annular top cover B30 that is detachably connected to the base B20. The insulating ring A22 is sandwiched between the bottom of the top cover B30 and the blind hole B40. The top cover B30 has a top cover hole B31 in the middle for inserting a pressure rod B10. The top cover hole B31 is aligned with the core direction of the central hole A221. The pressure rod B10 and the central hole A221, as well as the pressure rod B10 and the top cover hole B31, are clearance fits.

[0030] In the above scheme, the function of the pressing fixture is to process the battery sample and the insulating ring into a single battery sample assembly. The pressing rod B10 can be freely inserted into the top cover hole B31 and the middle hole A221. By applying pressure to the pressing rod B10 with a press, the battery sample A21 can be adhered to the bottom of the annular hole of the insulating ring A22. Afterwards, the top cover B30 can be removed to take out the battery sample assembly A20.

[0031] like Figure 9 As shown, the bottom surface of the blind hole B40 is a stepped surface, and a boss B21 protruding towards the top cover B30 is provided in the center of the bottom of the hole. The boss B21 and the stepped surface of the bottom of the blind hole B40 form an annular recess to accommodate the insulating ring A22. The diameter of the platform of the boss B21 is the same as the diameter of the central hole A221 of the insulating ring A22. In the above scheme, the annular recess can limit the insulating ring A22, so that the center of the insulating ring A22 coincides with the core of the top cover hole B31 of the top cover B30, thereby ensuring that the pressure rod B10 does not interfere with the insulating ring A22 when inserted. Among them, the stepped surface of the outer periphery of the annular recess can initially position the insulating ring A22, and the cooperation of the boss B21 and the central hole A221 completes the final positioning of the insulating ring A22. At this time, a small gap will remain between the outer peripheral wall of the insulating ring A22 and the stepped surface of the bottom of the blind hole B40.

[0032] In practice, first, place the insulating ring A22 within the annular recess formed between the boss B21 and the stepped surface at the bottom of the blind hole B40. Install the top cover B30, ensuring its bottom surface is in contact with the top surface of the insulating ring A22. Place the electrolyte and electrode material into the central hole A221 of the insulating ring A22, laying it on the boss B21. Then, insert the pressure rod B10 and apply pressure to adhere the battery sample A21 to the annular hole of the insulating ring A22. Next, remove the pressure rod B10, top cover B30, and insulating ring A22 in sequence. At this point, a thin cavity will be left at the rear end of the insulating ring A22, on the side that contacts the surface of the boss B21 before the battery sample A21. This cavity is formed by the height difference between the annular recess at the bottom of the blind hole B40 and the surface of the boss B21. After removing the insulating ring A22, fill this cavity with another electrode material to complete the entire battery sample assembly A20.

[0033] Preferably, the blind hole B40 has threads on its sidewall surface, forming a threaded engagement with the top cover B30, and the pressure rod B10 has a platform-shaped pressure head B11 on its top. The pressure head B11 facilitates the application of pressure to the top of the pressure rod B10 by the press.

Claims

1. A solid-state battery in-situ measurement device, wherein a through hole (10a) is provided in the middle of the housing (10) for X-rays to pass through from front to back, characterized in that: The rear cavity of the through hole (10a) accommodates the battery sample assembly (A20) to be tested. The battery sample assembly (A20) includes an insulating ring (A22) and a sheet-like battery sample (A21) disposed at the rear end of the central hole (A221) of the insulating ring (A22). The through hole (10a) and the central hole (A221) of the insulating ring (A22) form a through hole extending longitudinally. A tubular first electrode (30) with the core direction aligned with the core of the through hole (10a) and the central hole (A221) is inserted into the through hole from front to back. A plate-shaped second electrode (40) is provided on the housing (10) at the rear end of the through hole (10a). A front beryllium window plate (51) is attached to the front and rear sample surfaces of the battery sample (A21). The rear beryllium window plate (52) is formed, the rear end of the first electrode (30) is pressed against the front beryllium window plate (51), the front plate surface of the second electrode (40) is pressed against the rear beryllium window plate (52), the front end of the first electrode (30) is exposed in front of the housing (10), and the second electrode (40) has a light hole (401) corresponding to the area where the sample surface of the battery sample (A21) is located. Insulation is provided between the first electrode (30) and the second electrode (40).

2. The solid-state battery in-situ measurement device according to claim 1, characterized in that: The first electrode (30) is inserted into the cavity of the through hole (10a), and the outer tube wall and the inner wall of the through hole (10a) form a threaded fit.

3. The solid-state battery in-situ measurement device according to claim 1, characterized in that: The housing (10) includes a front cover (11), an insulating pad (12) and a rear cover (13) stacked sequentially from front to back, and the through holes in the middle of the three are connected in sequence to form a through hole (10a). The second electrode (40) is attached to the rear plate surface of the rear cover (13). The middle part of the rear cover (13) is an enlarged section of the through hole (10a) for accommodating the battery sample assembly (A20) to be tested.

4. The solid-state battery in-situ measurement device according to claim 3, characterized in that: A sealing ring (80) is provided between the front cover (11) and the insulating pad (12), between the insulating pad (12) and the rear cover (13), and between the rear cover (13) and the second electrode (40) or the rear beryllium window plate (52).

5. The solid-state battery in-situ measurement device according to claim 3, characterized in that: The front cover (11) has a cavity in the middle to accommodate the fixing ring (14). The inner hole of the fixing ring (14) and the outer tube wall at the corresponding position of the first electrode (30) form a threaded fit. The outer ring wall of the fixing ring (14) and the front cover (11) have corresponding pin holes (111). The pin holes (111) on the front cover (11) pass through the side wall of its cavity and the outer wall of the front cover (11). The core of the pin hole (111) is perpendicular to the core of the through hole (10a). A sealing ring (80) is provided between the fixing ring (14) and the insulating pad (12).

6. The solid-state battery in-situ measurement device according to claim 1, characterized in that: The first electrode (30) has a disc-shaped pressure head (31) at the suspension end of the through hole (10a) extending forward. A pressure cap (32) is provided on the front disc surface of the pressure head (31). A polyimide film (60) is sandwiched between the pressure head (31) and the pressure cap (32) and the film covers the X-ray penetration path. A stepped hole with a diameter larger than that of the through hole (10a) is provided in the middle of the front end face of the pressure head (31), and the pressure cap (32) is placed at the stepped hole. The stepped hole and the through hole (10a) extend sequentially through each other in the front and back directions.

7. The solid-state battery in-situ measurement device according to claim 3, characterized in that: The diameter of the front beryllium window plate (51) is the same as the diameter of the tube section into which the first electrode (30) is inserted (10a), and a sealing ring (80) is provided between the rear cover (13) and the rear beryllium window plate (52).

8. The solid-state battery in-situ measurement device according to claim 3, characterized in that: The front cover (11), insulating pad (12) and rear cover (13) are provided with corresponding front bolt holes (121), and the rear cover (13) and the second electrode (40) are provided with corresponding rear bolt holes (131).

9. The solid-state battery in-situ measurement device according to claim 3, characterized in that: The first electrode (30) extends forward from the suspension end of the through hole (10a) and the second electrode (40) has an insertion hole (132) for inserting an electrode rod (70). The core direction of the electrode rod (70) is perpendicular to the core of the through hole (10a). An "L"-shaped bracket (1) is connected to the side of the plate of the housing (10).

10. A pressing fixture for a solid-state battery in-situ measurement device according to any one of claims 1 to 9, characterized in that: The base (B20) has a blind hole (B40) in the middle to accommodate the insulating ring (A22). The bottom rear end of the central hole (A221) of the insulating ring (A22) is used to form a sheet-shaped battery sample (A21). The top of the base (B20) has an annular top cover (B30) that is detachably connected to the base (B20). The insulating ring (A22) is sandwiched between the top cover (B30) and the bottom of the blind hole (B40). The top cover (B30) has a top cover hole (B31) in the middle for inserting the pressure rod (B10). The core direction of the top cover hole (B31) is consistent with that of the central hole (A221). The pressure rod (B10) and the central hole (A221) and the pressure rod (B10) and the top cover hole (B31) are both clearance fits.

11. The tableting fixture according to claim 10, characterized in that: The bottom surface of the blind hole (B40) is a stepped surface, and a boss (B21) protruding towards the top cover (B30) is provided in the center of the bottom of the hole. The boss (B21) and the stepped surface of the bottom of the blind hole (B40) form an annular recess to accommodate the insulating ring (A22). The diameter of the boss (B21) is the same as the diameter of the central hole (A221) of the insulating ring (A22).

12. The tableting fixture according to claim 10, characterized in that: The blind hole (B40) has threads on its sidewall surface and forms a threaded engagement with the top cover (B30). The top of the pressure rod (B10) has a platform-shaped pressure head (B11).

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