Fixture for observing solid-state batteries

Abstract

To properly observe solid-state batteries using a microscopic Raman spectrometer.SOLUTION: A fixture 1 for observing solid-state batteries includes: a container 10; a holding part 20; and a quartz glass 30. The container 10 has a first internal space 11. The holding part 20 holds a solid-state battery 100 and is stored in the first internal space 11. The quartz glass 30 is arranged so as to face the solid-state battery 100 held by the holding part 20. The container 10 has a flow path 14 to introduce a low-active or inert gas 200 with respect to the solid-state battery 100 held by the holding part 20 to the first internal space 11 and circulate the gas in the first internal space. By using the fixture 1 for observing solid-state batteries, the influence of outside air on the solid-state battery 100 is suppressed with the circulation of the prescribed gas 200 and scattering light from the solid-state battery 100 is accurately detected through the quartz glass 30 in the observation using a microscopic Raman spectrometer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a tool for observing a solid-state battery. [Background technology]

[0002] A technique is known in which an all-solid-state battery sandwiched between a specified fixing jig is placed in an airtight observation container with a transparent window, and illumination light from a mercury lamp, a white light source, or the like is allowed to enter through the transparent window, thereby enabling microscopic observation of the all-solid-state battery during charging and discharging (Patent Document 1).

[0003] Also, a technique is known for performing Raman microscope observation using an observation sample sealed container equipped with an observation window material such as glass through which a sample chamber can be seen (Patent Document 2). Also, a technique is known in which an all-solid-state battery is polished while embedded in a resin such as an epoxy resin, and the polished cross section is subjected to Raman spectroscopic analysis using an argon laser (Patent Document 3).

[0004] Also, a technique is known in which a quartz optical window is applied to a coin cell of a lithium-ion battery for in situ Raman spectroscopic analysis (Patent Document 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2017-212163 A [Patent Document 2] JP 2012-233707 A [Patent Document 3] International Publication No. 2021 / 095757 Brochure [Patent Document 4] JP 2022-523977 A Summary of the Invention [Problem to be solved by the invention]

[0006] When observing the state of a solid-state battery using a Raman microscope, depending on the configuration of the jig used to hold the solid-state battery, it may not be possible to properly observe the solid-state battery, for example, to properly detect light scattered from the solid-state battery in a specified atmosphere or during charging or discharging.

[0007] In one aspect, the present invention aims to properly observe a solid-state battery using a Raman microspectrometer. [Means for solving the problem]

[0008] In one aspect, a solid-state battery observation tool is provided, comprising a container having a first internal space, a holding part that holds a solid-state battery and is accommodated in the first internal space, and quartz glass arranged to face the solid-state battery held in the holding part, wherein the container has a flow path for introducing and circulating a gas that is less active or inactive with respect to the solid-state battery held in the holding part into the first internal space. Effect of the Invention

[0009] In one aspect, it becomes possible to properly observe solid-state batteries using a Raman microspectrometer. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram (part 1) for explaining a configuration example of a jig for observing a solid-state battery. [Diagram 2] FIG. 2 is a diagram (part 2) for explaining a configuration example of the jig for observing a solid-state battery. [Diagram 3] FIG. 13 is a diagram (part 3) for explaining a configuration example of the jig for observing a solid-state battery. [Figure 4] FIG. 1 is a diagram showing an example of the results of measuring the charge / discharge characteristics of a solid-state battery. [Diagram 5] FIG. 13 is a diagram showing an example of the results of measuring the influence of gas inside a solid-state battery observation jig. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] 1 to 3 are diagrams for explaining a configuration example of a solid-state battery observation jig. Fig. 1 shows a schematic exploded perspective view of a main part of the solid-state battery observation jig. Fig. 2 shows a schematic external perspective view of a main part of the solid-state battery observation jig. Fig. 3 shows a schematic cross-sectional view of III-III in Fig. 2.

[0012] A solid-state battery observation jig 1 shown in FIGS. 1 to 3 is one example of a jig used for observing (microscopic Raman spectroscopy measurement) a solid-state battery 100 using a microscopic Raman spectroscopy device. 1 to 3 show schematic examples of a state in which a solid-state battery 100 to be observed is set in a solid-state battery observation jig 1. FIG.

[0013] Here, the solid-state battery 100 set in the solid-state battery observation jig 1 has a battery element 101 (power generation element) and a positive electrode terminal 102 and a negative electrode terminal 103 connected thereto, as shown in Fig. 3, for example. Although not shown here, the battery element 101 has a positive electrode layer which is an electrode layer containing a positive electrode active material and a solid electrolyte, etc., a negative electrode layer which is an electrode layer containing a negative electrode active material and a solid electrolyte, etc., and an electrolyte layer which is provided between the positive electrode layer and the negative electrode layer and contains a solid electrolyte. The positive electrode layer of the battery element 101 is connected to the positive electrode terminal 102, and the negative electrode layer of the battery element 101 is connected to the negative electrode terminal 103.

[0014] The solid-state battery observation tool 1 shown in FIGS. 1 to 3 includes a container 10, a holder 20, and quartz glass 30. The container 10 has a first internal space 11 formed by a bottom 12 and a side wall 13 rising from the bottom 12. Various insulating materials such as resin, glass, ceramics, etc. can be used for the container 10. The holding part 20 is housed in the first internal space 11 of the container 10.

[0015] The holder 20 holds the solid-state battery 100 to be observed. The holder 20 includes a pair of guides 21 that sandwich the solid-state battery 100, and a push-up block 22 that supports the solid-state battery 100 sandwiched between the pair of guides 21.

[0016] Each of the pair of guides 21 of the holding part 20 has a recess extending between the opposing surfaces. The recesses of each guide 21 form one recess 21a when the pair of guides 21 are arranged to sandwich the solid-state battery 100. The pair of guides 21 can be made of various insulating materials such as resin, glass, ceramics, etc.

[0017] The push-up block 22 of the holding part 20 is provided in the recesses 21a of the pair of guides 21, and supports the solid-state battery 100 sandwiched between the pair of guides 21. The push-up block 22 can be made of various insulating materials such as resin, glass, ceramics, etc. The push-up block 22 may be made of the same material as the pair of guides 21, or a different material may be used.

[0018] The pair of guides 21 of the holding part 20 are provided with through holes 21b for inserting the screws 110. The through holes 21b of each guide 21 may be screw holes into which the screws 110 can be screwed. The bottom 12 in the first internal space 11 of the container 10 is provided with screw holes (not shown) in which the screws 110 can be screwed, at positions corresponding to the through holes 21b of the pair of guides 21.

[0019] The holding unit 20 is accommodated in the first internal space 11 of the container 10 with the solid-state battery 100 sandwiched between the pair of guides 21 and with the push-up block 22 provided in the recess 21a. Then, the screw 110 is inserted into the through hole 21b of the guide 21, and the tip of the screw 110 is screwed into the screw hole in the bottom 12 of the container 10. In this manner, the holding unit 20 that holds the solid-state battery 100 is accommodated in the first internal space 11 of the container 10 with the push-up block 22 provided in the recess 21a of the pair of guides 21, and with the pair of guides 21 fixed to the container 10 by the screw 110.

[0020] The quartz glass 30 is disposed so as to face the solid-state battery 100 held in the holder 20 housed in the first internal space 11 of the container 10. For example, the quartz glass 30 having a thickness of about 1 mm is disposed so as to cover the solid-state battery 100 held in the holder 20 in the first internal space 11.

[0021] The quartz glass 30 functions as an observation window when the solid-state battery 100 held in the holder 20 in the first internal space 11 is observed with a Raman microscope. That is, light of a predetermined wavelength (excitation laser) used in the Raman microscope is incident on the solid-state battery 100 to be observed through the quartz glass 30 of the observation window, and scattered light from the solid-state battery 100 is detected through the quartz glass 30 of the observation window.

[0022] Furthermore, it can be said that the quartz glass 30 also functions as a pressing member that presses the solid-state battery 100 held in the holding portion 20 in the first internal space 11 against the bottom 12 of the container 10, or as a lid member that prevents the solid-state battery 100 held in the holding portion 20 from jumping out of the container 10.

[0023] A gas 200 that is low in activity or inactive to the solid-state battery 100 held in the holding part 20 is introduced into the container 10 from the outside (such as a gas introduction line 90 described later). The container 10 includes a flow path 14 for introducing and circulating such a predetermined gas 200 into the first internal space 11 that accommodates the holding part 20 that holds the solid-state battery 100. For example, the container 10 is provided with two flow paths 14 that penetrate the bottom 12 and communicate with the first internal space 11.

[0024] The gas 200 introduced into the first internal space 11 through the flow path 14, i.e., the gas 200 having low activity or inactivity with respect to the solid-state battery 100, may be, for example, dry air with a moisture content adjusted to a certain value or less, for example, dry air with a dew point in the range of −30° C. to −10° C. In addition, the gas 200 having low activity or inactivity with respect to the solid-state battery 100 may be gas such as nitrogen (N2) or argon (Ar).

[0025] A spring 15 is inserted into each of the two flow paths 14 of the container 10. One end of each spring 15 is fixed to a base portion 50 described below. For example, a coil spring is provided as the spring 15. Each spring 15 is disposed in the flow path 14 so that a predetermined gas 200 to be introduced into the first internal space 11 can flow. Note that the type of spring 15 is not limited to a coil spring, as long as the gas 200 can be introduced into the first internal space 11 through the flow path 14, that is, as long as the introduction of the gas 200 is not completely hindered by the spring 15.

[0026] When the holding portion 20 that holds the solid-state battery 100 is housed in the first internal space 11 of the container 10, each spring 15 comes into contact with a push-up block 22 provided in the recess 21a of the pair of guides 21. Each spring 15 that comes into contact with the push-up block 22 urges the push-up block 22 toward the solid-state battery 100 and the quartz glass 30. The push-up block 22 urged by the spring 15 has the function of urging the solid-state battery 100 sandwiched between the pair of guides 21 toward the quartz glass 30.

[0027] Two conductive probes 16 are provided in the container 10. The two probes 16 are provided in the bottom 12 of the container 10 so as to penetrate the bottom 12, with one end extending and protruding into the first internal space 11 and the other end extending and protruding outside the container 10 (into a second internal space 52 described below). The two probes 16 are supported by the bottom 12 of the container 10 at intermediate portions between both ends. The two probes 16 may be movable toward the quartz glass 30 side or the opposite side while being guided by the bottom 12 of the container 10 at the intermediate portion using a spring or the like.

[0028] The push-up block 22 of the holding part 20 is provided with through holes 22a through which one ends of the two probes 16 provided in the container 10 extend into the first internal space 11. When the holding part 20 holding the solid-state battery 100 is accommodated in the first internal space 11 of the container 10, the one ends of the two probes 16 are inserted into the through holes 22a of the push-up block 22 and electrically connected to the solid-state battery 100 sandwiched between the pair of guides 21. For example, the two probes 16 are electrically connected to the positive terminal 102 and the negative terminal 103 of the battery element 101 of the solid-state battery 100, respectively (FIG. 3).

[0029] One end of each of the two probes 16 extends into the first internal space 11 of the container 10 at a height according to the dimensions or position of the solid-state battery 100 sandwiched between the pair of guides 21 of the holder 20, and is connected to the positive terminal 102 and the negative terminal 103 of the solid-state battery 100. The solid-state battery 100 sandwiched between the pair of guides 21 of the holder 20 is urged toward the quartz glass 30 by the push-up block 22 urged by the spring 15, while maintaining the state in which the two probes 16 are connected.

[0030] The solid-state battery 100 , which is biased toward the quartz glass 30 by the push-up block 22 while the two probes 16 are kept connected, may be brought into contact with the quartz glass 30 . The solid state battery observation jig 1 shown in FIGS. 1 to 3 further includes a lid portion 40, a base portion 50, a packing 60, and a packing 70.

[0031] The lid part 40 is provided on the side of the container 10 on which the quartz glass 30 is disposed (on top of the container 10). The lid part 40 has an opening 41 that faces the quartz glass 30, as well as the holding part 20 and the solid-state battery 100 held therein. The lid part 40 can be made of various materials such as metal, resin, glass, ceramics, etc.

[0032] The quartz glass 30 is interposed between the opening 41 of the lid portion 40, and the holder 20 and the solid-state battery 100 held therein. The quartz glass 30 exposed from the opening 41 of the lid portion 40 functions as an observation window when the solid-state battery 100 held by the holder 20 in the first internal space 11 is observed with a Raman microscope.

[0033] A packing 60 is provided between the container 10 and the lid 40 on the outside of the quartz glass 30. The packing 60 may be made of a material such as resin. The lid 40 is placed on the container 10 via the quartz glass 30 and the packing 60 on its outside.

[0034] The solid-state battery 100 maintains a state in which the two probes 16 are connected to the quartz glass 30 side interposed between the container 10 and the lid portion 40 placed thereon, and is biased by a push-up block 22 biased by a spring 15.

[0035] The base part 50 is provided on the opposite side of the container 10 to the side where the quartz glass 30 is arranged (below the container 10). The base part 50 has an inlet 51 for introducing a low activity or inactive gas 200 from the outside into the solid-state battery 100. The base part 50 further has a second internal space 52 that communicates between the inlet 51 and the flow path 14 of the container 10. The predetermined gas 200 introduced from the inlet 51 of the base part 50 into the second internal space 52 is introduced from the second internal space 52 through the flow path 14 of the container 10 into the first internal space 11. The base part 50 can be made of various materials such as metal, resin, glass, ceramics, etc.

[0036] A packing 70 is provided between the base portion 50 and the container 10 outside the second internal space 52. The packing 70 may be made of a material such as resin. The container 10 is disposed on the base portion 50 via the packing 70.

[0037] Furthermore, the gaskets 60 and 70 may be capable of ensuring a level of airtightness that allows the first internal space 11 of the container 10 to be filled with a specified gas 200 introduced from the inlet 51 of the base portion 50, or to be able to create positive pressure.

[0038] One end of the spring 15 is fixed to the base portion 50. When the container 10 is placed on the base portion 50 via the packing 70, the other end of the spring 15, one end of which is fixed to the base portion 50, is inserted into the flow path 14 of the container 10.

[0039] When the holder 20 that holds the solid-state battery 100 is accommodated in the first internal space 11 of the container 10, one end of the spring 15 is fixed to the base portion 50 and the other end is inserted into the flow path 14 of the container 10, and the other end of the spring 15 abuts against the push-up block 22 of the holder 20. The push-up block 22 is urged toward the quartz glass 30 by the spring 15 that abuts against it. The solid-state battery 100 sandwiched between the pair of guides 21 of the holder 20 is urged toward the quartz glass 30 by the push-up block 22 that is urged by the spring 15.

[0040] A probe 16 is provided in the container 10 and has one end extending and protruding into the first internal space 11, and when the container 10 is placed on the base portion 50 via the gasket 70, the other end extends and protrudes into the second internal space 52.

[0041] When the holder 20 for holding the solid-state battery 100 is housed in the first internal space 11 of the container 10, one end of the probe 16 extending into the first internal space 11 is inserted into the through hole 22a of the push-up block 22 and connected to the solid-state battery 100 (its positive terminal 102 and negative terminal 103). The push-up block 22, which is biased by the spring 15, supports the solid-state battery 100 in a state connected to the probe 16, and biases it toward the quartz glass 30.

[0042] A lead wire outlet 53 is provided in the base portion 50. A lead wire 80 is electrically connected to the other end of the probe 16 extending into the second internal space 52 of the base portion 50, in which the container 10 is disposed via a packing 70. The lead wire 80 is drawn out from the lead wire outlet 53 of the base portion 50 to the outside.

[0043] A gas introduction line 90 for introducing a predetermined gas 200, i.e., a gas 200 that is low active or inactive with respect to the solid-state battery 100, is connected to the inlet 51 of the base part 50. The gas introduction line 90 may be provided with a valve 91 for adjusting the introduction of the predetermined gas 200 into the second internal space 52. The valve 91 provided in the gas introduction line 90 can also be said to be a valve 91 connected to the inlet 51 of the base part 50.

[0044] The flow rate of the gas 200 from the inlet 51 to the second internal space 52 is adjusted by the valve 91 provided in the gas inlet line 90. More specifically, the flow rate of the gas 200 is adjusted by the valve 91 provided in the gas inlet line 90, and the environment of the first internal space 11 into which the gas 200 is introduced from the second internal space 52 through the flow path 14 of the container 10, i.e., the atmosphere, internal pressure, etc. of the first internal space 11 are adjusted.

[0045] The lid 40, the packing 60, the container 10 and the packing 70 are provided with through holes 40a, 60a, 10a and 70a for inserting the screws 120 at corresponding positions, for example, at the four corners. The through holes 40a, 60a, 10a and 70a may be screw holes into which the screws 120 can be screwed. The base 50 is provided with screw holes 50a for screwing the screws 120 at positions corresponding to the through holes 40a, 60a, 10a and 70a.

[0046] The container 10 is placed on the base 50 via the packing 70, the holder 20 is housed in the first internal space 11, and the lid 40 is placed on top of the holder 20 via the quartz glass 30 and the packing 60. In this state, a screw 120 is inserted into the through hole 40a, the through hole 60a, the through hole 10a, and the through hole 70a. Then, the tip of the screw 120 is screwed into the screw hole 50a of the base 50. As a result, the lid 40, the packing 60, the quartz glass 30, the holder 20, the container 10, the packing 70, and the base 50 are integrated.

[0047] The solid-state battery 100 to be observed, which is set in the solid-state battery observation jig 1 as described above, is observed using a micro-Raman spectrometer, that is, micro-Raman spectroscopic measurement is performed. The solid-state battery 100 to be observed is polished in advance so as to expose a cross section where the electrode layers of the battery element 101, that is, the positive electrode layer and the negative electrode layer, and the electrolyte layer interposed therebetween, are laminated.

[0048] The cross section (also referred to as the "polished cross section") formed by polishing the solid-state battery 100 may include a positive electrode terminal 102 connected to the positive electrode layer exposed by polishing, and a negative electrode terminal 103 connected to the negative electrode layer exposed by polishing. The positive electrode terminal 102 and the negative electrode terminal 103 may be formed on the battery element 101 before polishing, or may be formed after the battery element 101 is polished.

[0049] In assembling the solid-state battery observation jig 1 in which the solid-state battery 100 is set, the container 10 is placed on the base part 50 via a packing 70. A lead wire 80 drawn out from a lead wire outlet 53 to the outside is connected to a probe 16 provided in the container 10 and extending into a second internal space 52 of the base part 50. A spring 15 fixed to the base part 50 is inserted into the flow path 14 of the container 10.

[0050] The polished solid-state battery 100 is sandwiched between a pair of guides 21 of the holder 20 so that the polished cross section faces the quartz glass 30. The pair of guides 21 sandwiching the solid-state battery 100 are housed in the first internal space 11 of the container 10 with the push-up blocks 22 provided in the recesses 21a, and are fixed to the container 10 using screws 110.

[0051] At this time, a probe 16 provided in the container 10 and extending into the first internal space 11 is inserted into the through hole 22a of the push-up block 22. The push-up block 22 is biased toward the solid-state battery 100 by a spring 15 fixed to the base portion 50 and inserted into the flow path 14 of the container 10.

[0052] A lid 40 is placed on the container 10 in which the holder 20 is housed, with the quartz glass 30 and a packing 60 interposed therebetween. The solid-state battery 100 sandwiched between a pair of guides 21 of the holder 20 is pressed against the probe 16 side and the push-up block 22 side by the quartz glass 30.

[0053] The positive terminal 102 and the negative terminal 103 of the solid-state battery 100 are connected to the probe 16 inserted into the through hole 22a of the push-up block 22. The solid-state battery 100 is biased toward the solid-state battery 100 side and the quartz glass 30 side by the push-up block 22 biased by the spring 15, while maintaining the state in which the probe 16 is connected.

[0054] The lid 40 , the packing 60 , the container 10 and the packing 70 are fixed to the base 50 using screws 120 . In this manner, the solid-state battery 100 having a polished cross section formed by polishing is set in the solid-state battery observation jig 1. Then, the solid-state battery observation jig 1 is set in a micro-Raman spectroscopic device, and micro-Raman spectroscopic measurement is performed on the solid-state battery 100 having the polished cross section formed.

[0055] In the microscopic Raman spectroscopy measurement, light of a predetermined wavelength is incident on the polished cross section of the solid-state battery 100 through the quartz glass 30 of the observation window exposed to the opening 41 of the lid 40. Scattered light from the solid-state battery 100 to which the predetermined light is incident on the polished cross section is detected through the quartz glass 30 of the observation window exposed to the opening 41 of the lid 40.

[0056] In the solid-state battery observation tool 1, the observation window is made of quartz glass 30, which reduces the adverse effect of the observation window material on the measurement results of scattered light compared to when an ordinary glass material is used for the observation window. Therefore, the scattered light from the solid-state battery 100 can be detected with high accuracy, and the state of the solid-state battery 100 can be properly observed.

[0057] Furthermore, in microscopic Raman spectroscopy using the solid-state battery observation tool 1, the solid-state battery 100 can be charged or discharged through the lead wire 80 and the probe 16 connected thereto. Therefore, in microscopic Raman spectroscopy using the solid-state battery observation tool 1, it is possible to cause light to be incident on the polished cross section of the solid-state battery 100 and to detect scattered light from the polished cross section while charging the solid-state battery 100. In microscopic Raman spectroscopy using the solid-state battery observation tool 1, it is possible to cause light to be incident on the polished cross section of the solid-state battery 100 and to detect scattered light from the polished cross section while discharging the solid-state battery 100.

[0058] By using a solid-state battery observation tool 1 having an observation window made of quartz glass 30 and capable of charging or discharging the solid-state battery 100 through a lead wire 80, the state of the solid-state battery 100 during charging or discharging can be observed accurately and appropriately.

[0059] In addition, in microscopic Raman spectroscopy using the solid-state battery observation tool 1, a specified gas 200 can be introduced into the solid-state battery observation tool 1 from a gas inlet line 90 connected to the inlet 51 of the base portion 50.

[0060] The gas 200 introduced from the gas introduction line 90 is introduced into the second internal space 52 of the base part 50, and then introduced into the first internal space 11 in which the solid-state battery 100 is housed, through the flow path 14 of the container 10, as shown by the dotted arrows in Fig. 3. The gas 200 introduced into the inside of the solid-state battery observation jig 1 is released to the outside from gaps present in the solid-state battery observation jig 1 (Fig. 3 shows, as an example, gaps between the lid part 40 and the container 10).

[0061] The introduced gas 200 adjusts the environment, such as the atmosphere and internal pressure, inside the solid-state battery observation jig 1 (first internal space 11), and the opening / closing or opening degree of a valve 91 provided in the gas introduction line 90 is adjusted so that the internal environment is maintained or roughly maintained.

[0062] In this manner, in the solid-state battery observation jig 1, a predetermined gas 200 is introduced from the gas introduction line 90, thereby making it possible to adjust the surrounding environment of the solid-state battery 100 accommodated in the first internal space 11 of the container 10. The gas 200 to be introduced into the first internal space 11 may be a gas 200 that is low in activity or inactive with respect to the solid-state battery 100. For example, the gas 200 to be introduced into the first internal space 11 may be dry air with a moisture content adjusted to a certain value or less, or may be nitrogen, argon, or the like.

[0063] In the solid-state battery observation jig 1, the environment surrounding the solid-state battery 100 can be filled with a gas 200 that is low in activity or inactive with respect to the solid-state battery 100. In the microscopic Raman spectroscopy measurement using the solid-state battery observation jig 1, it is possible to detect the incidence of light on the polished cross section of the solid-state battery 100 placed in such an environment filled with the predetermined gas 200 and the scattered light from the polished cross section. Alternatively, it is possible to detect the incidence of light on the polished cross section of the solid-state battery 100 placed in such an environment filled with the predetermined gas 200 and the scattered light from the polished cross section while charging or discharging the solid-state battery 100.

[0064] According to the solid-state battery observation tool 1, in the microscopic Raman spectroscopy measurement, the state of the solid-state battery 100 can be observed accurately and appropriately while suppressing the influence of the outside air on the solid-state battery 100. Alternatively, the state of the solid-state battery 100 during charging or discharging can be observed accurately and appropriately while suppressing the influence of the outside air on the charging or discharging of the solid-state battery 100.

[0065] Next, the results of an investigation into the effects of using the solid-state battery observation tool 1 having the above-mentioned configuration will be described. FIG. 4 is a diagram showing an example of the results of measuring the charge / discharge characteristics of a solid-state battery.

[0066] 4(A) to 4(C) show an example of the charge / discharge characteristics when the solid-state battery 100 is charged and discharged under predetermined conditions. In FIG. 4(A) to FIG. 4(C), the horizontal axis represents the capacity [μAh], and the vertical axis represents the voltage [V]. Charging is performed by the constant current-constant voltage (CCCV) method, with the current condition being 0.1 mA, the voltage condition being 3.5 V, and the charging time being 5 hours. Discharging is performed by the constant voltage (CV) method, with the current condition being 0.1 mA, and the end voltage condition being 0 V.

[0067] 4(A) shows, for comparison, an example of the charge / discharge characteristics of a solid-state battery 100 that has not been polished, i.e., a solid-state battery 100 that does not have a polished cross section, when the battery is charged and discharged without using the solid-state battery observation jig 1 ("No polishing", "No jig"). The charge / discharge is performed at a temperature of 23° C. in a dry air environment.

[0068] 4(B) shows an example of the charge / discharge characteristics of the polished solid-state battery 100, i.e., the solid-state battery 100 with a polished cross section, when the charge / discharge was performed without using the solid-state battery observation jig 1 ("with polishing" and "without jig"). The charge / discharge was performed in an environment of a temperature of 23°C and a relative humidity of 50% (50% RH).

[0069] 4(C) shows an example of the charge / discharge characteristics of the polished solid-state battery 100, i.e., the solid-state battery 100 with a polished cross section, when the battery is charged and discharged using the above-mentioned jig for solid-state battery observation 1 ("with polishing" and "with jig"). The charge / discharge was performed in an environment of a temperature of 23°C and a relative humidity of 50% (50% RH).

[0070] As can be seen from Fig. 4(B), proper charge / discharge characteristics may not be obtained when measuring the charge / discharge characteristics of the polished solid-state battery 100 in a constant humidity environment. On the other hand, as can be seen from Fig. 4(C), when the above-mentioned solid-state battery observation jig 1 is used, proper measurement results can be obtained even when measuring the charge / discharge characteristics of the polished solid-state battery 100 in a constant humidity environment.

[0071] As described above, the solid-state battery 100 is held by the holding portion 20, which is housed in the first internal space 11 of the container 10, and the positive terminal 102 and the negative terminal 103 of the solid-state battery 100 are connected to the probe 16. According to the solid-state battery observation jig 1, the charge / discharge characteristics of the solid-state battery 100 whose cross section has been formed by polishing can be properly evaluated.

[0072] FIG. 5 is a diagram showing an example of the results of measuring the influence of gas inside a solid-state battery observation jig. Figure 5 shows the change over time in weight of the moisture absorbent placed inside the solid-state battery observation jig 1 with and without gas introduction. Here, calcium chloride (CaCl2), which has strong water absorption, is used as the moisture absorbent. Dry air with a dew point in the range of -30°C to -10°C is used as the gas. In Figure 5, the horizontal axis represents time [h], and the vertical axis represents the weight change [mg] of the moisture absorbent.

[0073] As shown in L1 of FIG. 5, when dry air is not introduced into the solid-state battery observation jig 1, that is, when outside air enters the solid-state battery observation jig 1, the weight of the moisture absorbent tends to increase monotonically with the passage of time.

[0074] On the other hand, as shown by L2 in FIG. 5, when dry air is constantly introduced into the solid-state battery observation jig 1, the weight of the moisture absorbent tends to increase monotonically over time, but the rate (slope) of weight increase is significantly reduced.

[0075] As shown by L3 in FIG. 5, when dry air is introduced into the solid-state battery observation jig 1 for a certain period of time (0-24 h) and then the introduction of dry air is stopped for a certain period of time thereafter (24-70 h), the weight of the moisture absorbent tends to increase at a rate greater than that before the introduction of dry air was stopped.

[0076] The solid-state battery 100 can be placed in a relatively low moisture environment by introducing dry air into the solid-state battery observation jig 1. Then, the solid-state battery 100 placed in such an environment can be subjected to microscopic Raman spectroscopy measurement, or the solid-state battery 100 can be subjected to microscopic Raman spectroscopy measurement while charging or discharging.

[0077] By using the solid-state battery observation tool 1 and performing microscopic Raman spectroscopy while introducing dry air, the state of the solid-state battery 100 or the state of the solid-state battery 100 during charging or discharging can be properly observed while suppressing the effects of moisture in the outside air.

[0078] Although dry air is used as an example here, the same effect can be obtained by using nitrogen or argon. Furthermore, when nitrogen or argon is used, deterioration of the solid-state battery 100 caused by oxygen (O2, O) during microscopic Raman spectroscopy measurement, charging, or discharging can be further suppressed, making it possible to observe the state of the solid-state battery 100.

[0079] As described above, according to the solid-state battery observation tool 1, the quartz glass 30 is used for the observation window, so that the scattered light from the solid-state battery 100 can be accurately detected in the microscopic Raman spectroscopy measurement, and the state of the solid-state battery 100 can be properly observed.

[0080] Furthermore, by configuring the solid-state battery observation jig 1 to be capable of charging or discharging the solid-state battery 100, the state of the solid-state battery 100 during charging or discharging can be accurately and appropriately observed in microscopic Raman spectroscopy measurement.

[0081] Furthermore, by configuring the solid-state battery observation tool 1 to be capable of introducing a low activity or inactive gas into the solid-state battery 100, the state of the solid-state battery 100 or the state during charging or discharging can be accurately and appropriately observed while suppressing the influence of outside air in the microscopic Raman spectroscopy measurement.

[0082] According to the microscopic Raman spectroscopy measurement of the solid-state battery 100, it is possible to accurately observe an image of the polished cross section of the solid-state battery 100. According to the microscopic Raman spectroscopy measurement of the solid-state battery 100 during charging or discharging, it is possible to obtain information regarding the peak shift of scattered light for the components contained in the battery element 101 during charging or discharging of the solid-state battery 100. Furthermore, based on the information regarding the peak shift, it is possible to obtain information regarding the behavior of the components contained in the battery element 101 during charging or discharging of the solid-state battery 100, for example, the behavior of lithium ions, negative electrode active material, positive electrode active material, etc. during charging or discharging (such as insertion and release of lithium ions into and from the positive electrode active material and negative electrode active material).

[0083] Proper observation of the state of the solid-state battery 100 by microscopic Raman spectroscopy is effective for the development and manufacture of the solid-state battery 100. The solid-state battery observation tool 1 is useful for obtaining proper information on the state of the solid-state battery 100 by microscopic Raman spectroscopy. [Explanation of symbols]

[0084] 1. Solid-state battery observation tool 10 containers 10a, 21b, 22a, 40a, 60a, 70a through hole 11 1st interior space 12 Bottom 13 Side wall 14 Flow Path 15 Spring 16 Probes 20 Holding part 21 Guide 21a Recess 22 Push-up block 30 Quartz glass 40 Lid 41 Opening 50 Base 50a screw hole 51 Introduction 52 Second interior space 53 Lead wire exit 60, 70 Gasket 80 Lead Wire 90 Gas introduction line 91 Valve 100 solid state battery 101 Battery elements 102 Positive terminal 103 Negative terminal 110, 120 Screw 200 Gas

Claims

1. a container having a first interior space; A holding portion that holds a solid-state battery and is housed in the first internal space; a quartz glass arranged to face the solid-state battery held by the holding part; Including, The container is provided with a flow path for introducing a gas that is less active or inactive with respect to the solid-state battery held in the holding portion into the first internal space and circulating the gas.

2. The solid-state battery observation tool according to claim 1 , wherein the container further comprises a probe electrically connected to the solid-state battery held in the holding portion.

3. The container further includes a lid portion that is disposed on the quartz glass side and has an opening that faces the solid-state battery held by the holding portion, The solid-state battery observation tool according to claim 1 , wherein the quartz glass is interposed between the opening and the solid-state battery.

4. 2. The solid-state battery observation tool according to claim 1, further comprising a base portion arranged on the opposite side of the container from the quartz glass side, the base portion having the gas inlet and a second internal space communicating with the gas inlet and the flow path.

5. The solid-state battery observation tool according to claim 4 , wherein a valve for regulating the introduction of the gas is connected to the inlet of the base portion.

6. 2. The solid-state battery observation tool according to claim 1, wherein the solid-state battery has a stacked electrode layer and an electrolyte layer, and is held by the holding part so that a surface on which the electrode layer and the electrolyte layer are stacked faces the quartz glass.

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