Split type all-solid-state battery test mold

Abstract

The utility model provides a split type all-solid-state battery test die. The split type all-solid-state battery testing die comprises a stainless steel clamp, an upper die head, an insulating battery sleeve and a lower die head. The split type all-solid-state battery testing mold has the advantages of being simple in structure, small in size, light in weight and the like, testing can be conducted within the temperature range of 25-250 DEG C, and the highest bearing pressure reaches up to 500 Mpa; the ceramic inner cavity can be separated from other components and is subjected to heat treatment together with the solid electrolyte sheet; the all-solid-state battery test mold can be used for a lithium ion all-solid-state battery, a sodium ion all-solid-state battery, a zinc ion all-solid-state battery, a magnesium ion all-solid-state battery, a fluorine ion all-solid-state battery and a chloride ion all-solid-state battery.

Description

Technical Field

[0001] The utility model relates to the field of all-solid-state battery testing, in particular to a split all-solid-state battery testing mold. Background Art

[0002] Lithium-ion batteries, with their unique advantages such as high energy density, long cycle life, low self-discharge, and fast charging, are widely used in various electronic devices and electric vehicles. However, the rapid development of lithium resources has also exposed numerous problems with lithium-ion batteries. For example, lithium-ion batteries are expensive to manufacture and require specialized charging equipment. Furthermore, lithium-ion batteries have a limited service life, with performance degrading after a certain number of charge and discharge cycles. Furthermore, the safety of traditional liquid lithium-ion batteries has a certain upper limit and is prone to thermal runaway, even fire or explosion, under extreme conditions such as overcharge, over-discharge, or high temperatures. Furthermore, the energy density of lithium-ion batteries with liquid electrolytes has reached its upper limit, making it difficult to meet future demands for higher energy density.

[0003] To improve safety and further increase energy density, solid-state batteries have emerged. Solid-state batteries replace liquid electrolytes with solid electrolytes, greatly reducing the risk of thermal runaway. The performance indicators of solid-state electrolytes, such as reduction stability, oxidation stability, and thermal stability, are all superior to those of liquid electrolytes. Therefore, solid-state batteries are regarded as an important development direction for the next generation of battery technology, which is expected to solve the safety accident problems of traditional liquid lithium batteries and meet the demand for higher energy density. Although the research on solid-state battery technology has progressed rapidly, its technical maturity in practical application still needs to be improved compared with traditional lithium-ion batteries, especially the testing methods of all-solid-state batteries still need to be improved.

[0004] All-solid-state batteries are composed of a positive electrode, a negative electrode, and an electrolyte, which are pressed into tablets respectively. The contact between the electrode / electrolyte interface is poor, and usually a large pressure is required to enhance the interface contact. Compared with traditional liquid electrolytes, the migration rate of conductive ions in solid electrolytes is slower, and it is necessary to increase the ionic conductivity at higher temperature conditions. Therefore, all-solid-state batteries pose higher requirements for battery testing devices, namely high temperature and high pressure. For example, the Chinese invention patent (CN 201910197405.1) discloses a method for preparing an all-solid-state battery and its mold. After pressing the positive and negative electrodes and the electrolyte into tablets, they are transferred to a button cell for encapsulation, and pressurized testing cannot be achieved. The Chinese invention patent (CN 201710821957.6) discloses an all-solid-state battery mold that can provide a pressure of up to 200 Mpa and can be tested in the temperature range of -90°C to 250°C, but battery systems with higher pressures cannot be evaluated. The Chinese utility model patent (CN 202222466425.4) discloses an all-solid-state battery testing mold, in which an adjusting screw is added above the pressing plate to control the pressure of the battery, with a complex structure and a cumbersome process. As is well known, the ionic conductivity of solid electrolytes can be improved through heat treatment. For the above-mentioned disclosed invention or utility model patents, the heat treatment process requires taking out the pressed electrolyte tablet and transferring it to a heating furnace, which is cumbersome and easily damages the surface of the electrolyte tablet.

[0005] Therefore, it is necessary to develop a new type of solid electrolyte mold that can achieve high-temperature heat treatment without damaging the electrolyte surface. Summary of the Utility Model

[0006] Aiming at the deficiencies of the prior art, the utility model provides a split-type all-solid-state battery testing mold, which can withstand high temperature, high pressure, and acid-base corrosion; the ceramic inner cavity in the mold can be separated from other components and heat-treated together with the solid electrolyte tablet; in addition, the mold cooperates with a multi-channel electrochemical workstation to evaluate various performances of the all-solid-state battery.

[0007] In order to achieve the above purpose, the technical solution adopted by the utility model is:

[0008] A split-type all-solid-state battery test mold, including a stainless-steel fixture, an upper die head, an insulating battery sleeve, and a lower die head. The stainless-steel fixture includes a base and a top plate arranged in parallel. Between the base and the top plate, multiple columns are evenly distributed along the circumferential side to fix the base and the top plate. On the upper side of the top plate, there are multiple nuts to fix the columns in appropriate positions to provide the required pressure. On the top side of the upper die head, there is an upper die head insulating base. On the side of the upper die head, there is a positive electrode conductive metal rod. On the bottom side of the upper die head, there is an upper die head sealing nut. Under the upper die head sealing nut, there is an upper die head sealing ring pressing ring. Under the upper die head sealing ring pressing ring, there is an upper die head sealing ring. The insulating battery sleeve includes a ceramic inner cavity and a ceramic mold body shell. The ceramic inner cavity is placed inside the ceramic mold body shell. On the bottom side of the ceramic inner cavity, there is a ceramic sealing ring. Under the ceramic sealing ring, there is a ceramic sealing nut. On the bottom side of the lower die head, there is a lower die head insulating base. On the side of the lower die head, there is a negative electrode conductive metal rod. On the upper end of the lower die head, there is a lower die head sealing ring.

[0009] Preferably, the stainless-steel fixture is made of 304 stainless steel.

[0010] Preferably, the base and the top plate have the same size, and the shape can be circular. There are three columns evenly distributed along the circumferential side between the base and the top plate. The base and the top plate can also be square in shape, and there are four columns evenly distributed along the circumferential side between the base and the top plate.

[0011] Preferably, the columns can be circular, square, or a combination of both.

[0012] Preferably, the number of nuts is the same as the number of columns.

[0013] Preferably, the upper die head insulating base is made of polyether ether ketone (PEEK).

[0014] Preferably, the outer diameter of the upper die head matches the aperture size of the ceramic inner cavity.

[0015] Preferably, the positive electrode conductive metal rod is made of iron, copper, aluminum, or silver.

[0016] Preferably, the length of the positive electrode conductive metal rod is greater than the radius of the top plate.

[0017] Preferably, the upper die head sealing nut is made of PEEK.

[0018] Preferably, the upper die head sealing ring pressing ring is made of PEEK.

[0019] Preferably, the upper die head sealing ring is made of one of nitrile rubber, silicone rubber, or fluororubber, preferably fluororubber.

[0020] Preferably, the material of the ceramic inner cavity is zirconia;

[0021] Preferably, the aperture of the ceramic inner cavity is 6 - 12 mm; Optionally, the aperture of the ceramic inner cavity can be 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm or 12 mm, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable;

[0022] Preferably, the material of the ceramic mold body shell is PEEK;

[0023] Preferably, the material of the lower die head insulating base is PEEK;

[0024] Preferably, the material of the ceramic sealing ring is one of nitrile rubber, silicone rubber or fluororubber, preferably fluororubber;

[0025] Preferably, the ceramic sealing ring is placed in the groove of the lower die head insulating base;

[0026] Preferably, the material of the ceramic sealing nut is PEEK;

[0027] Preferably, the material of the negative conductive metal rod includes iron, copper, aluminum or silver;

[0028] Preferably, the length of the negative conductive metal rod is greater than the radius of the base;

[0029] Preferably, the material of the lower die head sealing ring is one of nitrile rubber, silicone rubber or fluororubber, preferably fluororubber;

[0030] As the preferred technical solution described in the first aspect of the present invention, the technical solution includes:

[0031] A split-type all-solid-state battery test mold, including a stainless steel fixture made of 304 material, an upper die head, an insulating battery sleeve, and a lower die head. The stainless steel fixture includes a base and a top plate arranged in parallel with the same size. Between the base and the top plate, 3-4 columns are evenly distributed along the circumferential side to fix the base and the top plate. On the upper side of the top plate, there are 3-4 nuts to fix the columns in appropriate positions to provide the required pressure. On the top side of the upper die head, there is an upper die head insulating base made of PEEK material. On the side of the upper die head, there is a positive electrode conductive metal rod made of iron, copper, aluminum, or silver. On the bottom side of the upper die head, there is an upper die head sealing nut made of PEEK material. Under the upper die head sealing nut, there is an upper die head sealing ring pressing ring made of PEEK material. Under the upper die head sealing ring pressing ring, there is an upper die head sealing ring made of fluororubber material. The insulating battery sleeve includes a zirconia ceramic inner cavity with a pore diameter of 6-12 mm and a ceramic mold body shell made of PEEK material. The zirconia ceramic inner cavity is placed inside the ceramic mold body shell. On the bottom side of the zirconia ceramic inner cavity, there is a ceramic sealing ring made of fluororubber material. Under the ceramic sealing ring, there is a ceramic sealing nut made of PEEK material. On the bottom side of the lower die head, there is a lower die head insulating base made of PEEK material. On the side of the lower die head, there is a negative electrode conductive metal rod made of iron, copper, aluminum, or silver. On the upper end of the lower die head, there is a lower die head sealing ring made of fluororubber material.

[0032] The all-solid-state battery test mold provided by the present utility model can be used for lithium-ion all-solid-state batteries, sodium-ion all-solid-state batteries, zinc-ion all-solid-state batteries, magnesium-ion all-solid-state batteries, fluoride-ion all-solid-state batteries, and chloride-ion all-solid-state batteries.

[0033] During use, the negative electrode material, solid electrolyte, and positive electrode material of the all-solid-state battery can be sequentially added to the solid battery mold, and then pressed into a sandwich-like sheet structure under the assistance of a press at a pressure of 500 Mpa.

[0034] The numerical ranges described in the present utility model not only include the point values exemplified above, but also include any point values between the above numerical ranges that are not exemplified. Due to space limitations and for the sake of simplicity, the present utility model will not exhaustively list the specific point values included in the described ranges.

[0035] Compared with the prior art, the present application has the following advantages:

[0036] 1. By using the zirconia ceramic inner cavity, the inner wall of the present utility model is smooth and easy to clean, which can ensure the safety of the battery under the conditions of high temperature of 250 °C and high pressure of 500 Mpa, and has strong acid and alkali corrosion resistance.

[0037] 2. The present utility model separates the zirconia ceramic inner cavity from other components of the solid battery mold, which is convenient to directly transfer the pressed electrolyte sheet together with the zirconia ceramic inner cavity for high-temperature heat treatment.

[0038] 3. The mold structure of the all-solid-state battery of the present utility model is simple, small in volume and light in weight. Description of the Drawings

[0039] Figure 1 The front view of the split all-solid-state battery test mold provided for Example 1;

[0040] Figure 2 The sectional view of the insulating battery sleeve of the split all-solid-state battery test mold provided for Example 1;

[0041] Figure 3 The schematic diagram of the usage scenario of the mold provided by the present utility model;

[0042] Figure 4 The electrochemical impedance performance test chart for Example 1;

[0043] Figure 5 The constant current charge and discharge performance test chart for Example 1;

[0044] Reference numerals: 1 - base, 2 - top plate, 3 - column, 4 - nut, 5 - lower die head insulating base, 6 - negative electrode conductive metal rod, 7 - ceramic sealing nut, 8 - ceramic die body shell, 9 - upper die head sealing nut, 10 - positive electrode conductive metal rod, 11 - upper die head insulating base, 12 - lower die head, 13 - lower die head sealing ring, 14 - ceramic sealing ring, 15 - ceramic inner cavity, 16 - upper die head sealing ring, 17 - upper die head sealing ring pressing ring, 18 - upper die head, 19 - insulating battery sleeve, 20 - stainless steel clamp. Detailed Embodiments

[0045] For a better understanding of the content of the present application, the following further illustrates the present application through the drawings and the best embodiments. The embodiments are only used to explain the present application and will not constitute any limitation to the present application.

[0046] Unless otherwise defined, all technical terms and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0047] Example 1

[0048] As Figure 1 shown, the present application provides an all-solid-state battery test mold, including a stainless steel clamp 20, an upper die head 18, an insulating battery sleeve 19, and a lower die head 12.

[0049] The stainless-steel fixture includes a base 1 and a top plate 2 which are arranged in parallel and have the same size. Both the base 1 and the top plate 2 are circular. Three holes are evenly opened on the base 1 and the top plate 2. Three columns 3 are evenly distributed along the circumferential side between the base 1 and the top plate 2 to fix the base 1 and the top plate 2. The upper end of the column 3 is provided with a thread that matches a nut 4 to fix the column in a proper position to provide the required pressure. The lower end of the column 3 is provided with a square area for easy disassembly of the tool; As Figure 2 shown, an upper die head insulating base 11 made of PEEK material is provided on the top side of the upper die head 18. A positive conductive metal rod 10 made of iron, copper, aluminum or silver is provided beside the upper die head 18. The lower end of the upper die head 18 is provided with a cylindrical metal rod whose size matches the inner diameter of the ceramic inner container 15. A PEEK material upper die head sealing nut 9 is provided on the bottom side of the upper die head 18. A PEEK material upper die head sealing ring pressing ring 17 is provided on the bottom side of the upper die head sealing nut 9. A fluororubber material upper die head sealing ring 16 is provided on the bottom side of the upper die head sealing ring pressing ring 17; The insulating battery sleeve is cylindrical, including a zirconia ceramic inner cavity 15 with a pore diameter of 10 mm and a ceramic mold body shell 8 made of PEEK material. The zirconia ceramic inner cavity 15 is placed inside the ceramic mold body shell 8. A fluororubber material ceramic sealing ring 14 is provided on the bottom side of the zirconia ceramic inner cavity 15. A PEEK material ceramic sealing nut 7 is provided on the bottom side of the ceramic sealing ring 14; A PEEK material lower die head insulating base 5 is provided on the bottom side of the lower die head 12. A negative conductive metal rod 6 made of iron, copper, aluminum or silver is provided beside the lower die head 12. A fluororubber material lower die head sealing ring 13 is provided at the upper end of the lower die head 12. The lower die head sealing ring 13 is placed in the upper groove of the lower die head 12.

[0050] The all-solid-state battery mold is used for an all-solid-state fluoride ion battery. The assembly method of the all-solid-state battery mold is to sequentially place a negative electrode (Sn foil), a solid electrolyte powder (200 mg PbSnF4), and a positive electrode (a mixture of 3 mg FeF3, 6 mg PbSnF4, and 1 mg conductive carbon) into the all-solid-state battery mold. Then, the three materials are pressed together under 500 Mpa by borrowing a press. Next, according to Figure 3 shown, the all-solid-state battery mold is placed in an oven and heated to 150 °C, and tested by connecting an electrochemical workstation (blue electricity channel).

[0051] As Figure 4 shown, under the conditions of an amplitude of 5 mV, a test frequency range of 100 mHz to 100 KHz, and a test temperature range of 150 °C, the electrochemical impedance spectrogram of the Sn|PbSnF4|FeF3 battery shows a shape similar to a semicircle in the high-frequency region, indicating the interfacial resistance between the electrode surface and the electrolyte surface; it shows a straight line in the low-frequency region, indicating the diffusion resistance and internal contact resistance of the electrolyte ions in the electrode pores.

[0052] AsFigure 5 As shown, in a high-temperature environment of 150 °C, the Sn|PbSnF4|FeF3 battery can obtain a discharge specific capacity of 129 mAh / g at a current density of 0.1C, and the first charge capacity is 91 mAh / g, showing good electrochemical performance.

[0053] The preferred embodiments of the present invention have been specifically described above, but the present invention is not limited to the described embodiments. Those skilled in the art can also make various equivalent variations or substitutions without departing from the spirit of the present invention, and these equivalent variations or substitutions are all included within the scope defined by the claims of this application.

Claims

1. A split-type all-solid-state battery test mold, characterized in that The all-solid-state battery test mold includes a stainless-steel fixture, an upper die head, an insulating battery sleeve, and a lower die head. The stainless-steel fixture includes a base and a top plate arranged in parallel. A plurality of columns are evenly distributed along the circumferential side between the base and the top plate to fix the base and the top plate. On the upper side of the top plate, there are a plurality of nuts to fix the columns in appropriate positions to provide the required pressure. On the top side of the upper die head, there is an upper die head insulating base. On the side of the upper die head, there is a positive conductive metal rod. On the bottom side of the upper die head, there is an upper die head sealing nut. Under the upper die head sealing nut, there is an upper die head sealing ring pressing ring. Under the upper die head sealing ring pressing ring, there is an upper die head sealing ring. The insulating battery sleeve includes a ceramic inner cavity and a ceramic mold body shell. The ceramic inner cavity is placed inside the ceramic mold body shell. On the bottom side of the ceramic inner cavity, there is a ceramic sealing ring. Under the ceramic sealing ring, there is a ceramic sealing nut. On the bottom side of the lower die head, there is a lower die head insulating base. On the side of the lower die head, there is a negative conductive metal rod. On the upper end of the lower die head, there is a lower die head sealing ring.

2. The all-solid-state battery test mold according to claim 1, wherein The stainless-steel fixture is made of 304 stainless steel. The base and the top plate have the same size and are circular in shape. Three columns are evenly distributed along the circumferential side between the base and the top plate. The base and the top plate are square in shape, and four columns are evenly distributed along the circumferential side between the base and the top plate. The shape of the column includes circular and / or square. The number of the nuts is the same as the number of the columns.

3. The all-solid-state battery test mold according to claim 2, wherein The upper die head insulating base is made of polyether ether ketone (PEEK). The outer diameter of the upper die head matches the aperture size of the ceramic inner cavity. The material of the positive conductive metal rod on the side of the upper die head includes iron, copper, aluminum, or silver. The length of the positive conductive metal rod on the side of the upper die head is greater than the radius of the top plate. The upper die head sealing nut is made of PEEK. The upper die head sealing ring pressing ring is made of PEEK. The upper die head sealing ring is made of one of nitrile rubber, silicone rubber, or fluororubber.

4. The all-solid-state battery test mold according to claim 1, wherein The ceramic inner cavity is made of zirconia. The aperture of the ceramic inner cavity is 6 - 12 mm. The ceramic mold body shell is made of PEEK.

5. The all-solid-state battery test mold according to claim 1 or 4, characterized in that, The lower die head insulating base is made of PEEK. The ceramic sealing ring is made of one of nitrile rubber, silicone rubber, or fluororubber. The ceramic sealing ring is placed in the groove of the lower die head insulating base. The ceramic sealing nut is made of PEEK. The material of the negative conductive metal rod includes iron, copper, aluminum, or silver. The length of the negative conductive metal rod is greater than the radius of the base. The lower die head sealing ring is made of one of nitrile rubber, silicone rubber, or fluororubber.

6. The all-solid-state battery test mold according to claim 5, characterized in that, The all-solid-state battery test mold includes a 304 stainless steel fixture, an upper die head, an insulating battery sleeve, and a lower die head. The stainless steel fixture includes a base and a top plate that are parallelly arranged and have the same size. Between the base and the top plate, 3-4 columns are evenly distributed along the circumferential side to fix the base and the top plate. On the upper side of the top plate, there are 3-4 nuts to fix the columns in appropriate positions to provide the required pressure. On the top side of the upper die head, there is an upper die head insulating base made of PEEK material. Beside the upper die head, there is a positive electrode conductive metal rod made of iron, copper, aluminum, or silver. On the bottom side of the upper die head, there is an upper die head sealing nut made of PEEK material. Under the upper die head sealing nut, there is an upper die head sealing ring pressing ring made of PEEK material. Under the upper die head sealing ring pressing ring, there is an upper die head sealing ring made of fluororubber material. The insulating battery sleeve includes a zirconia ceramic inner cavity with a pore diameter of 6-12 mm and a ceramic mold body shell made of PEEK material. The zirconia ceramic inner cavity is placed inside the ceramic mold body shell. On the bottom side of the zirconia ceramic inner cavity, there is a ceramic sealing ring made of fluororubber material. Under the ceramic sealing ring, there is a ceramic sealing nut made of PEEK material. On the bottom side of the lower die head, there is a lower die head insulating base made of PEEK material. Beside the lower die head, there is a negative electrode conductive metal rod made of iron, copper, aluminum, or silver. On the upper end of the lower die head, there is a lower die head sealing ring made of fluororubber material.

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