All-solid-state battery reaction chamber for in-situ Raman test

Abstract

The utility model relates to an all-solid-state battery reaction chamber for an in-situ Raman test. The problem that an existing all-solid-state battery detection device is complex in structure is solved. According to the technical scheme, the all-solid-state battery reaction chamber comprises a reaction chamber shell, a battery containing chamber is formed in the reaction chamber shell, and all-solid-state batteries are filled in the battery containing chamber; an observation window is arranged at the top of the battery accommodating chamber; charge-discharge connecting assemblies are arranged on two sides of the reaction chamber shell, and one end, far away from the reaction chamber shell, of each charge-discharge connecting assembly is connected with charge-discharge equipment. According to the utility model, the all-solid-state battery is placed in the battery accommodating chamber, a Raman light path penetrates through the observation window and is focused on the all-solid-state battery, and meanwhile, a Raman system collects Raman scattering light and the Raman scattering light is recorded by a spectrograph; the device is simple in structure and convenient to detect; an observation window is designed at the top of the reaction chamber shell, so that the reaction and change of the interface position between the solid electrolyte and the positive and negative electrodes in the battery can be observed, and the detection range is large.

Description

Technical Field

[0001] The utility model relates to the technical field of in-situ Raman testing of all-solid-state batteries, and in particular to an all-solid-state battery reaction chamber for in-situ Raman testing. Background Art

[0002] All-solid-state batteries have multiple advantages over traditional liquid batteries. All-solid-state batteries use solid electrolytes instead of liquid electrolytes, which reduces the risk of battery leakage, combustion or explosion and improves battery safety.

[0003] Solid-state electrolytes have a wide electrochemical window, and solid-state batteries can use higher voltage cathode materials, thereby increasing the energy density of the entire battery. In addition, all-solid-state batteries are usually able to operate normally over a wider temperature range because the chemical and thermal properties of solid-state electrolytes are relatively more stable. Therefore, all-solid-state batteries have broad application prospects in the field of new energy vehicles. However, at present, all-solid-state batteries have interface reactions between solid electrolytes and positive and negative electrode materials, metal negative electrode interface dendrite growth, and interface contact cracking during the charging and discharging process of all-solid-state batteries. These phenomena will reduce the cycle stability of all-solid-state batteries, thereby seriously affecting the energy performance of all-solid-state batteries. How to detect the interface deterioration phenomenon between solid-state electrolytes and positive and negative electrode materials during the battery charging and discharging process is of great significance for guiding the next step of all-solid-state battery design.

[0004] Raman spectroscopy is a non-destructive analytical technique that generates spectra based on the interaction between incident lasers and chemical bonds within materials. It can provide detailed information on the chemical structure, phase and morphology, crystallinity, and molecular interactions at the interface between the solid electrolyte and the positive and negative electrodes in all-solid-state batteries. Since most mainstream solid electrolytes such as sulfides (such as Li2S-P2S5-based systems), polymer solid electrolytes (such as systems containing LiTFSI salts), and halide systems (such as Li3YCl6 systems) are sensitive to air and humidity, all-solid-state batteries need to be assembled or tested and characterized under inert gas.

[0005] The Chinese invention patent with publication number "CN113030138A" and patent name "A full-solid-state battery reaction chamber and test method for in-situ XRD and Raman testing" and the utility model patent with authorization announcement number "CN216958150U" and patent name "A full-solid-state battery reaction chamber system for in-situ Raman testing" are both in-situ detection devices that use Raman spectroscopy to detect solid-state batteries, but they are only set on one side of the positive and negative electrodes of the solid-state battery, and can only observe the reaction occurring on one side, and cannot explore the reaction and products at the interface.

[0006] The invention patent with publication number "CN115791741A" and patent name "Dual-window in-situ Raman detection device and detection method for solid-state lithium-ion batteries" can observe the reactions and products at the interface; however, the device has a complex structure, in which the optical coupling element is heavy flint glass, and needs to be matched with a stainless steel tube with the help of a refractive index matching liquid. This design will lose the Raman spectrum signal.

[0007] The utility model patent with announcement number "CN 216958150 U" and patent name "A fully solid-state battery reaction chamber system for in-situ Raman testing" has a complex battery reaction chamber structure involving multiple components. The screw in the comparative document is made of pressure-resistant stainless steel and only plays the role of applying pressure, not as a conductive electrode; the observation window is a translucent quartz sheet. In order to ensure the mechanical integrity during the sealing process, its thickness cannot be reduced to the micron level, which reduces the penetration of the light emitted by the high-magnification Raman lens. The position recognition ability is general under the high-magnification lens, and the Raman signal of the reflected light is also weak. Utility Model Content

[0008] The utility model provides an all-solid-state battery reaction chamber for in-situ Raman testing, which has a simple structure, is easy to assemble, is suitable for in-situ Raman spectrum detection of all-solid-state batteries of various shapes, and has a large detection range.

[0009] In order to overcome the problems existing in the prior art, the technical solution adopted by the utility model is: an all-solid-state battery reaction chamber for in-situ Raman testing, comprising a reaction chamber shell, a reaction chamber base is provided at the bottom of the reaction chamber shell, a U-shaped groove is provided on the upper surface of the reaction chamber base, a battery accommodating chamber is opened inside the reaction chamber shell, and the battery accommodating chamber is filled with an all-solid-state battery. After the reaction chamber shell and the reaction chamber base are superimposed, the U-shaped groove is arranged in the battery accommodating chamber, and the all-solid-state battery is arranged in the U-shaped groove; an observation window is arranged on the top of the all-solid-state battery; charging and discharging connection components are provided on both sides of the reaction chamber shell, and the charging and discharging connection components connect the all-solid-state battery and the charging and discharging equipment.

[0010] Furthermore, the charging and discharging connection assembly is two fastening bolts, which pass through two threaded holes symmetrically opened on both sides of the reaction chamber shell and are respectively connected to the positive and negative electrodes of the all-solid-state battery; the connection direction of the two fastening bolts is parallel to the slotting direction of the U-shaped groove.

[0011] Furthermore, metal pads are respectively connected to the positive and negative poles of the all-solid-state battery, and each fastening bolt contacts the metal pads respectively.

[0012] Furthermore, an annular groove is provided at the bottom of the reaction chamber shell, and a sealing ring is provided in the annular groove.

[0013] Furthermore, a circular groove is provided on the top of the reaction chamber shell; the observation window is a disc structure and is arranged in the circular groove.

[0014] Furthermore, glue is applied in the circular groove, and the observation window is bonded to the reaction chamber shell by the glue.

[0015] Furthermore, a plurality of threaded holes are vertically opened on the reaction chamber base, a countersunk hole is arranged at the bottom of the reaction chamber shell relative to the threaded holes, and the reaction chamber base is connected to the reaction chamber shell through a plurality of hexagonal bolts.

[0016] Furthermore, the material of the fastening bolt is a high-conductivity copper alloy.

[0017] Furthermore, the material of the observation window is PET resin.

[0018] Compared with the prior art, the utility model has the following advantages:

[0019] 1. The utility model designs two fastening bolts on both sides of the reaction chamber shell. The bolts are made of highly conductive copper. In addition to the pressure-applying function, they also play a conductive role. They can not only achieve connection with the positive and negative electrodes of the all-solid-state battery, but also be used to fix the all-solid-state battery, which is easy to operate. A circular groove is provided on the top of the reaction chamber shell, and the observation window is a disc structure. The connection stability of the two is high, and the flatness of the reaction chamber surface is also improved. The designed PET material observation window effectively enhances the light penetration and the reflected Raman signal, and achieves the advantages of more accurate position recognition and stronger Raman signal under a high-magnification lens, and a large detection range.

[0020] 2. The utility model is provided with a U-shaped groove on the reaction base, and the all-solid-state battery is placed in the U-shaped groove, which is easy to install. The U-shaped groove design is convenient for the charge and discharge connection assembly to connect the positive and negative electrodes of the all-solid-state battery from the two ends of the groove of the U-shaped groove. At the same time, the reaction chamber shell and the reaction chamber base are connected by setting a hexagonal bolt and a sealing ring. The connection is convenient and tight, and it is easy to disassemble. The sealing ring also realizes the sealing function to ensure the airtightness of the battery accommodating chamber.

[0021] 3. The utility model provides two metal pads in the all-solid-state battery, and uses square metal pads to clamp the solid-state battery, so that solid-state batteries of any shape or cut solid-state batteries can be observed;

[0022] 4. The utility model has a simple structure, is easy to assemble, and has low cost. It is suitable for in-situ Raman spectroscopy detection of all-solid-state batteries of different shapes and has a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is an exploded view of an all-solid-state battery reaction chamber for in-situ Raman testing of the utility model;

[0024] Figure 2 This is an exploded view of an all-solid-state battery reaction chamber for in-situ Raman testing of the utility model;

[0025] Figure 3 This is an assembly diagram of an all-solid-state battery reaction chamber for in-situ Raman testing of the utility model;

[0026] Figure 4 This is the in-situ Raman laser spectrum of the first charge and discharge at the positive electrode interface of the NCM / Li6PS5Cl / Li all-solid-state battery.

[0027] Description of the drawings: 1. Observation window; 2. Metal pad; 3. All-solid-state battery; 4. Reaction chamber housing; 5. Fastening bolts; 6. Sealing ring; 7. Reaction chamber base; 8. Hexagonal bolts; DETAILED DESCRIPTION

[0028] The following will be combined with the drawings in the embodiments of the utility model to clearly and completely describe the technical solutions in the embodiments of the utility model. Obviously, the described embodiments are only part of the embodiments of the utility model, not all of the embodiments. Based on the embodiments of the utility model, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the utility model.

[0029] The utility model provides an all-solid-state battery reaction chamber for in-situ Raman testing, such as Figure 1-3 As shown, it includes a reaction chamber shell 4, an all-solid-state battery 3, an observation window 1, a charge and discharge connection assembly and a reaction chamber base 7. A battery accommodating chamber is provided inside the reaction chamber shell 4, and the battery accommodating chamber is filled with an all-solid-state battery 3; an observation window 1 is provided on the top of the battery accommodating chamber; charge and discharge connection assemblies are provided on both sides of the reaction chamber shell 4, and the charge and discharge connection assemblies connect the all-solid-state battery 3 and the charge and discharge equipment; when performing in-situ Raman spectroscopy detection, the all-solid-state battery 3 is placed in the battery accommodating chamber, and then the charge and discharge connection assembly is connected to it; after the connection is completed, the Raman light path passes through the observation window 1 and is focused onto the all-solid-state battery 3 for Raman spectroscopy detection.

[0030] As an implementation method in this embodiment, a reaction chamber base 7 is provided at the bottom of the reaction chamber shell 4, and a mounting U-shaped groove is provided on the reaction chamber base 7. The all-solid-state battery 3 is placed in the mounting U-shaped groove, which is convenient for installation; and the mounting U-shaped groove design facilitates the charging and discharging connection components to connect the positive and negative electrodes of the all-solid-state battery 3 from both ends of the groove of the mounting U-shaped groove.

[0031] As an implementation method in this embodiment, a circular groove is provided on the top of the reaction chamber shell 4; the observation window 1 is a disc structure, and the material is PET resin; the use of the observation window 1 made of high-transmittance PET material can enhance the Raman spectrum signal and improve the detection effect. The disc structure is arranged in the circular groove, and this design can ensure the connection stability between the two; at the same time, it also improves the flatness of the reaction chamber surface. Glue is applied in the circular groove, and the observation window 1 is bonded to the reaction chamber shell 4 through the glue.

[0032] As an implementation method in this embodiment, the charge and discharge connection assembly includes two fastening bolts 5, the material of the fastening bolts 5 is a high-conductivity copper alloy, the two fastening bolts 5 pass through two threaded holes symmetrically opened on both sides of the reaction chamber shell 4 and are respectively connected to the positive and negative electrodes of the all-solid-state battery 3; and the direction of the connection line of the two fastening bolts 5 is parallel to the groove direction of the installation U-shaped groove, and the two fastening bolts 5 are rotated so that the two move toward each other along the groove direction of the installation U-shaped groove until they abut against the positive and negative electrodes at both ends of the all-solid-state battery 3; at the same time, the two fastening bolts 5 fix the all-solid-state battery 3. This design simultaneously realizes the connection and fixation of the positive and negative electrodes of the battery through the two fastening bolts 5, and has a simple structure and is easy to use.

[0033] As an implementation method in this embodiment, two metal pads 2 are respectively connected to the positive and negative sides of the all-solid-state battery 3; the two fastening bolts 5 are screwed into the battery accommodating chamber from both sides of the reaction chamber shell 4, and respectively abut the two metal pads 2, and the two fastening bolts 5 rotate, respectively pushing the two metal pads 2 to move toward each other along the installation U-shaped groove to clamp and fix the all-solid-state battery 3; the metal pads 2 are designed to ensure good conductivity between the two fastening bolts 5 and the positive and negative poles of the all-solid-state battery 3, and the metal pads 2 can also disperse the force of the fastening bolts 5 on the all-solid-state battery 3, to prevent the clamping force generated during the rotation of the fastening bolts 5 from being too large to cause damage to the all-solid-state battery 3.

[0034] As an implementation method in this embodiment, a plurality of threaded holes are vertically opened on the reaction chamber base 7, and hexagonal bolts 8 are installed in each of the threaded holes; the reaction chamber base 7 is connected to the reaction chamber shell 4 through the plurality of hexagonal bolts 8, which is convenient to connect and easy to disassemble.

[0035] As an implementation method in this embodiment, an annular groove is provided on the connection surface between the reaction chamber shell 4 and the reaction chamber base 7, and a sealing ring 6 is provided in the annular groove. The sealing ring 6 is designed to ensure the airtightness of the battery accommodating chamber. Figure 2 shown.

[0036] The working principle of this embodiment is:

[0037] like Figure 3As shown, when the all-solid-state battery reaction chamber of this embodiment is used, the all-solid-state battery 3 is placed in the installation U-shaped groove, and metal pads 2 are placed at both ends, and the reaction chamber shell 4 is connected to the reaction chamber base 7. The fastening bolts 5 on both sides of the reaction chamber shell 4 are rotated so that they are screwed into the battery accommodating chamber from both ends and respectively abut on the two metal pads 2. Start the in-situ Raman detection, first debug the Raman optical path system to ensure that the incident light is focused on the all-solid-state battery 3 through the observation window 1; the detection light beam is required to achieve a spatial resolution of less than 2 microns; the positive and negative electrodes of the charging and discharging equipment are connected to the assembled fastening bolts 5 for charging and discharging; at the same time, the Raman system collects Raman scattered light in real time and records it by the spectrometer.

[0038] The Raman optical imaging diagram of the cross section of the pressed solid electrolyte Li6PS5Cl was observed through the observation window. The first charge and discharge at the positive electrode interface of the NCM / Li6PS5Cl / Li all-solid-state battery was performed using the all-solid-state battery reaction chamber provided in this embodiment. The in-situ Raman laser spectrum was obtained, as shown in FIG. Figure 4 shown.

[0039] In the above description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the protection scope of the present invention is not limited to the specific embodiments disclosed above.

[0040] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may be subject to various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An all-solid-state battery reaction chamber for in-situ Raman testing, comprising a reaction chamber housing (4), characterized in that: A reaction chamber base (7) is provided at the bottom of the reaction chamber shell (4), a U-shaped groove is provided on the upper surface of the reaction chamber base (7), a battery accommodating chamber is provided inside the reaction chamber shell (4), an all-solid-state battery (3) is loaded in the battery accommodating chamber, the U-shaped groove is provided in the battery accommodating chamber after the reaction chamber shell (4) and the reaction chamber base (7) are superimposed, and the all-solid-state battery (3) is provided in the U-shaped groove; an observation window (1) is provided on the upper part of the all-solid-state battery (3); charging and discharging connection components are provided on both sides of the reaction chamber shell (4), and the charging and discharging connection components connect the all-solid-state battery (3) and the charging and discharging equipment.

2. The all-solid-state battery reaction chamber for in-situ Raman testing according to claim 1, characterized in that: The charging and discharging connection assembly comprises two fastening bolts (5), which pass through two threaded holes symmetrically opened on both sides of the reaction chamber shell (4) and are respectively connected to the positive and negative electrodes of the all-solid-state battery (3); the connection direction of the two fastening bolts (5) is parallel to the slotting direction of the U-shaped slot.

3. An all-solid-state battery reaction chamber for in-situ Raman testing according to claim 1 or 2, characterized in that: Metal pads (2) are connected to the positive and negative electrodes of the all-solid-state battery (3), respectively, and each fastening bolt (5) contacts the metal pads (2).

4. The all-solid-state battery reaction chamber for in-situ Raman testing according to claim 3, characterized in that: The bottom of the reaction chamber shell (4) is provided with an annular groove, and a sealing ring (6) is provided in the annular groove.

5. The all-solid-state battery reaction chamber for in-situ Raman testing according to claim 4, characterized in that: The top of the reaction chamber shell (4) is provided with a circular groove; the observation window (1) is a disc structure and is arranged in the circular groove.

6. The all-solid-state battery reaction chamber for in-situ Raman testing according to claim 5, characterized in that: Glue is applied inside the circular groove, and the observation window (1) is bonded to the reaction chamber shell (4) by the glue.

7. The all-solid-state battery reaction chamber for in-situ Raman testing according to claim 6, characterized in that: The reaction chamber base (7) is vertically provided with a plurality of threaded holes, and a countersunk hole is provided at the bottom of the reaction chamber shell (4) opposite to the threaded holes. The reaction chamber base (7) is connected to the reaction chamber shell (4) via a plurality of hexagonal bolts (8).

8. The all-solid-state battery reaction chamber for in-situ Raman testing according to claim 7, characterized in that: The material of the fastening bolt (5) is a high-conductivity copper alloy.

9. The all-solid-state battery reaction chamber for in-situ Raman testing according to claim 8, characterized in that: The material of the observation window (1) is PET resin.

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