Solid-state battery in-situ measuring device and tabletting tool thereof

Abstract

The invention provides a solid-state battery in-situ measuring device and a tabletting tool thereof. A through hole is formed in the middle of a shell of the measuring device, and a battery sample assembly is contained in a rear-section hole cavity of the through hole; a first electrode is inserted in the through hole, and a second electrode is arranged on the shell at the rear end of the through hole. A blind hole for accommodating an insulating ring is formed in the middle of a base of the tabletting tool, the insulating ring is clamped between a top cover and the bottom of the blind hole, and a top cover hole for inserting a pressing rod is formed in the middle of the top cover. According to the invention, a blind hole is formed in a tabletting tool, and a battery sample is adhered to the bottom of a ring hole of an insulating ring through pressurization of a pressing rod. When an experiment is carried out, the battery sample assembly is placed in the hole cavity of the through hole of the battery in-situ measurement device, so that the battery sample assembly is more convenient to take and place and has no risk of damage.

Description

Technical Field

[0001] The present invention relates to the technical field of battery in-situ characterization testing, and in particular to a solid-state battery in-situ measurement device and a tablet pressing tool thereof. Background Art

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

[0003] In the prior art, when conducting in-situ measurement experiments on solid-state batteries, a small disc-shaped battery sample is typically pressed using a tablet press. This sample is then placed and clamped within a battery in-situ measurement device. The battery in-situ measurement device includes components such as a battery sample mounting platform, positive and negative electrode terminals, a mounting seat, and a transmission window. The battery sample is assembled with a solid electrolyte, positive electrode material, and negative electrode material using a dedicated solid-state mold. The entire sample is then transferred to the interior of the solid-state in-situ cell and mounted on the mounting platform. A certain amount of pressure must be applied to ensure effective and close contact between the electrode materials, otherwise it will affect the phase change process and conductive properties of the battery material. Existing patents such as CN10A4393223A, KR2020110A000384U, and US9022652B2 all include components for applying pressure to the battery sample. However, these technologies make it difficult to control the pressure applied to the battery sample. Furthermore, due to the small size of the disc-shaped battery sample, it is difficult to control the pressure during placement and pressurization, resulting in breakage. Summary of the Invention

[0004] The primary purpose of the present invention is to provide a solid-state battery in-situ measurement device that is convenient for taking and placing battery samples and can ensure the integrity of the battery samples.

[0005] Another object of the present invention is to provide a tablet pressing tool that can press and assemble the battery sample assembly required by the above-mentioned measuring device.

[0006] In order to achieve the above-mentioned purpose, the technical solution adopted by the present invention is as follows: a through hole is provided in the middle of the shell for X-rays to pass through from front to back, and the rear cavity of the through hole accommodates the battery sample assembly to be tested, and the battery sample assembly includes an insulating ring and a sheet-shaped battery sample arranged at the rear end of the middle hole of the insulating ring; the through hole and the middle hole of the insulating ring constitute a through hole extending in the front-to-back direction, and a tubular first electrode with a core direction consistent with the through hole and the middle hole core is inserted into the through hole from front to back, and a plate-shaped second electrode is provided on the shell at the rear end of the through hole, and 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 is pressed against the front beryllium window plate, and the front plate surface of the second electrode is pressed against the rear beryllium window plate, and the front end of the first electrode is exposed in front of the shell, and the second electrode is provided with a light hole corresponding to the area where the sample surface of the battery sample is located, and insulation is provided between the first electrode and the second electrode.

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

[0008] The present invention mainly provides a blind hole for accommodating an insulating ring and a battery sample on a sheeting tool, applies pressure through a pressure rod so that the battery sample adheres to the bottom of the hole of the insulating ring, and processes the battery sample and the insulating ring into an integral battery sample assembly. When conducting an experiment, the battery sample assembly is placed in the cavity of the through hole of the battery in-situ measurement device so that the battery sample is located on the penetration path or diffraction path of the X-ray. Since the volume of the battery sample assembly composed of the battery sample and the insulating ring is much larger than that of a traditional small disc-shaped battery sample, when taking and placing, one only needs to hold the insulating ring without directly touching the battery sample, which makes taking and placing more convenient and without the risk of damage. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 、 5 The isometric views of the front and back of the solid-state battery in-situ measurement device are shown respectively;

[0010] Figure 2 、 6 They are Figure 1 Cross-section at the middle LL and MPN;

[0011] Figure 3 for Figure 2 A partial enlarged view of the K point in the middle;

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

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

[0014] Figure 8 This is an isometric view of the tablet press tooling;

[0015] Figure 9 It is a cross-sectional view of the tablet pressing tool;

[0016] Figure 10 for Figure 9 A partial enlarged view of the middle J;

[0017] Figure 11 This is the in-situ battery charge and discharge test diagram;

[0018] Figure 12 In-situ XAFS test data DETAILED DESCRIPTION

[0019] See also Figures 1 to 7 The solid-state battery in-situ measurement device shown in FIG. has a through hole 10a in the middle of the housing 10 for X-rays to pass through from front to back. The rear portion of the through hole 10a accommodates a 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 middle hole A221 of the insulating ring A22 form a through hole extending in the front-to-back direction. A tubular first electrode 30 with the core direction consistent with the through hole 10a and the middle hole A221 is inserted into the through hole from front to back. A plate-shaped second electrode 40 is provided on the shell 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 shell 10. The second electrode 40 is provided with a light-passing hole 401 corresponding to the area where the sample surface of the battery sample A21 is located. Insulation is set between the first electrode 30 and the second electrode 40.

[0021] In the above scheme, the battery sample A21 is pressed together with the insulating ring A22 through a sheeting tool to form a battery sample assembly A20. X-rays pass through the polyimide film 60, the front beryllium window plate 51, the battery sample A21 and the rear beryllium window plate 52 in the through hole 10a to conduct transmission mode or fluorescence mode experiments. The beryllium window plate has conductive properties, and the metal beryllium can be passed through by X-rays. One of the first electrode 30 and the second electrode 40 is connected to the positive pole of the power supply, and the other electrode is connected to the negative pole of the power supply, that is, electricity is passed between the first electrode 30, the front beryllium window plate 51, the battery sample A21, the rear beryllium window plate 52 and the second electrode 40. Since the volume of the battery sample assembly A20 is much larger than that of traditional small disc-shaped battery samples, when taking and placing, one only needs to hold the insulating ring A22 without directly touching the battery sample A21, which is more convenient to take and place and there is no risk of damage. 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 clamped 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, ensuring its conductive performance under the measurement state.

[0022] In order to facilitate the pressurization of battery sample A21, the first electrode 30 is inserted into the outer tube wall of the through hole 10a and forms a threaded fit with the inner hole wall of the through hole 10a. By rotating the outer tube wall of the first electrode 30 using the screw principle, the front beryllium window plate 51 can be pressed to provide pressure to the battery sample A21, which is convenient for manual operation, and the pressure is controllable and reliable. Figure 11 、 Figure 12 They are the in-situ battery charge and discharge test diagrams and in-situ XAFS test data diagrams obtained using the solid-state battery in-situ measurement device.

[0023] More specifically, the housing 10 comprises a front cover 11, an insulating gasket 12, and a rear cover 13, stacked in sequence from front to back. The through-holes in the middle of these three components connect to form a through-hole 10a. The second electrode 40 rests against the rear surface of the rear cover 13. The center of the rear cover 13 forms an expanded section of the through-hole 10a, which accommodates the battery sample assembly A20 under test. The insulating gasket 12 isolates the front cover 11 from the rear cover 13, preventing electrical shorting between the first electrode 30 and the second electrode 40 through the housing 10. The insulating gasket 12 is typically made of plastic.

[0024] Preferably, the front and rear sides of the battery sample A21 are respectively clamped by the front beryllium window plate 51 and the rear beryllium window plate 52. The diameter of the front beryllium window plate 51 is consistent with the diameter of the tube section of the first electrode 30 inserted into 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, when conducting the experiment, the front cover 11, the insulating gasket 12 and the rear cover 13 are first separated, and then the battery sample assembly A20 is filled into the expanded diameter section of the through hole 10a in the center of the rear cover 13. Then, the insulating gasket 12 and the front cover 11 are installed in sequence, and 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 is pressed against the front beryllium window plate 51, and the second electrode 40 is installed on the rear plate surface of the rear cover 13 so that it is in contact with the rear beryllium window plate 52.

[0025] In order to seal the battery sample A21, sealing rings 80 are set between the front cover 11 and the insulating gasket 12, between the insulating gasket 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 is not in contact with the outside world.

[0026] A more preferred solution is to provide a concave cavity in the middle of the front cover 11 to accommodate the fixing ring 14. The inner hole of the fixing ring 14 forms a threaded fit 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 are provided with corresponding pin holes 111. The pin holes 111 on the front cover 11 pass through the side wall of the concave 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 process threads on the inner hole wall of the fixing ring 14. Inserting a pin in the pin hole 111 can limit the circumferential position of the fixing ring 14.

[0027] Preferably, a disc-shaped indenter 31 is provided at the suspended end of the first electrode 30 extending forward from the through-hole 10a. A pressure cap 32 is provided on the front disk surface of the indenter 31. A polyimide film 60 is sandwiched between the indenter 31 and the pressure cap 32, and the film covers the X-ray penetration path. A stepped hole with a larger aperture than the aperture of the through-hole 10a is provided in the middle of the front end surface of the indenter 31, and the pressure cap 32 is placed on the stepped hole. The stepped hole and the through-hole 10a extend in the front-to-back direction. The indenter 31 facilitates the operator to rotate the first electrode 40 to apply pressure to the battery sample A21, and the indenter 31 also provides space for installing the polyimide film 60.

[0028] More specifically, corresponding front bolt holes 121 are provided between the front cover 11, the insulating gasket 12, and the rear cover 13, while corresponding rear bolt holes 131 are provided between the rear cover 13 and the second electrode 40. Insertion holes 132 for receiving the electrode rod 70 are provided at the overhanging end of the first electrode 30 extending forward from the through-hole 10a and at the side edge of the second electrode 40. The core 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 this embodiment, bolts in the front bolt holes 121 securely connect the front cover 11, the insulating gasket 12, and the rear cover 13, while bolts in the rear bolt holes 131 securely connect the rear cover 13 and the second electrode 40. The housing 10 is secured to a workbench via the bracket 1.

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

[0030] In the above scheme, the pressing tooling is used to form the battery sample and insulating ring into a single, integrated battery sample assembly. The pressing rod B10 can be freely inserted into the top cover hole B31 and the center hole A221. Using a press to apply pressure to the pressing rod B10, the battery sample A21 adheres to the bottom of the hole in the insulating ring A22. The top cover B30 can then be removed to remove 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 is provided in the center of the bottom of the hole, protruding toward the top cover B30. The boss B21 and the stepped surface at the bottom of the blind hole B40 form an annular recessed platform that accommodates the insulating ring A22. The diameter of the boss B21 surface is consistent with the diameter of the center hole A221 of the insulating ring A22. In the above scheme, the annular recessed platform can limit the position of the insulating ring A22, so that the center of the insulating ring A22 remains aligned 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 during insertion. The stepped surface on the outer periphery of the annular recessed platform can initially position the insulating ring A22, and the cooperation between the boss B21 and the center 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 at the bottom of the blind hole B40.

[0032] To do this, 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 abuts the top of the insulating ring A22. Place the electrolyte and electrode material within the center hole A221 of the insulating ring A22, laying them 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. The pressure rod B10, top cover B30, and insulating ring A22 are then removed in sequence. A thin recessed cavity is now formed on the side of the insulating ring A22 where the rear end of the hole contacts the surface of the boss B21. This recessed 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, the cavity is filled with another electrode material to complete the battery sample assembly A20.

[0033] Preferably, the side wall of the blind hole B40 is provided with a thread and is threadedly engaged with the top cover B30, and the top of the pressure rod B10 is provided with a table-shaped pressure head B11. The setting of the pressure head B11 can facilitate the press to apply pressure to the top of the pressure rod B10.

Claims

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

3. The solid-state battery in-situ measurement device according to claim 1, characterized in that: The housing (10) comprises a front cover (11), an insulating pad (12) and a rear cover (13) which are stacked in sequence from front to rear, 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), and the middle part of the rear cover (13) is an expanded diameter section of the through hole (10a) for accommodating a battery sample assembly (A20) to be tested.

4. The solid-state battery in-situ measurement device according to claim 3, characterized in that: 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).

5. The solid-state battery in-situ measurement device according to claim 3, characterized in that: A concave cavity for accommodating a fixing ring (14) is provided in the middle of the front cover (11); an inner hole of the fixing ring (14) is threadedly engaged with an outer tube wall at a corresponding position of the first electrode (30); corresponding pin holes (111) are provided on the outer ring wall of the fixing ring (14) and the front cover (11); the pin hole (111) on the front cover (11) passes through the side wall surface of the concave cavity and the outer wall surface of the front cover (11); and the core of the pin hole (111) is perpendicular to the core of the through hole (10a); and 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: A disc-shaped pressure head (31) is provided at the suspended end of the first electrode (30) extending forward from the through hole (10a), a pressure cover (32) is provided on the front disk surface of the pressure head (31), a polyimide film (60) is sandwiched between the pressure head (31) and the pressure cover (32), and the film covers the X-ray penetration path, a stepped hole with a larger aperture than that of the through hole (10a) is provided in the middle of the front end surface of the pressure head (31), and the pressure cover (32) is placed at the stepped hole, and the stepped hole and the through hole (10a) are connected in a front-to-back direction.

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 consistent with the diameter of the tube section of the first electrode (30) inserted into the through hole (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: Mutually corresponding front bolt holes (121) are provided between the front cover (11), the insulating pad (12) and the rear cover (13), and mutually corresponding rear bolt holes (131) are provided between the rear cover (13) and the second electrode (40).

9. The solid-state battery in-situ measurement device according to claim 3, characterized in that: A plug-in hole (132) for plugging in an electrode rod (70) is provided at the suspended end of the first electrode (30) extending forward from the through hole (10a) and at the side plate edge of the second electrode (40). The hole core direction of the electrode rod (70) is perpendicular to the hole core of the through hole (10a). An "L"-shaped bracket (1) is connected to the side surface of the plate of the shell (10).

10. A tablet pressing tool for the solid-state battery in-situ measurement device according to any one of claims 1 to 9, characterized in that: A blind hole (B40) for accommodating an insulating ring (A22) is provided in the middle of the base (B20); the rear end of the bottom of the middle hole (A221) of the insulating ring (A22) is used to form a sheet-shaped battery sample (A21); the top of the base (B20) is provided with an annular top cover (B30) detachably connected to the base (B20); the insulating ring (A22) is clamped between the top cover (B30) and the bottom of the blind hole (B40); a top cover hole (B31) for inserting a pressure rod (B10) is provided in the middle of the top cover (B30); the top cover hole (B31) and the middle hole (A221) have the same hole core direction; the pressure rod (B10) and the middle hole (A221), as well as the pressure rod (B10) and the top cover hole (B31) are clearance fits.

11. The tablet pressing tool according to claim 10, characterized in that: The bottom surface of the blind hole (B40) is a stepped surface, and a boss (B21) is provided in the center of the bottom of the hole, protruding toward the top cover (B30). The boss (B21) and the stepped surface of the bottom of the blind hole (B40) form an annular recessed platform for accommodating the insulating ring (A22). The diameter of the boss (B21) is consistent with the diameter of the center hole (A221) of the insulating ring (A22).

12. The tablet pressing tool according to claim 10, characterized in that: The side wall surface of the blind hole (B40) is provided with a thread and forms a threaded fit with the top cover (B30); the top of the pressure rod (B10) is provided with a table-shaped pressure head (B11).

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