NMR measurement cell and NMR measurement probe

Abstract

In an NMR measurement cell, two conductors for charging and discharging are provided that are interchangeable while ensuring airtightness inside the cell. [Solution] A battery sample is housed inside the cell body 64. A first pin 74 equipped with two O-rings 110 and 112 is inserted into a first pin hole 106 formed in the cell body 64. A second pin 78 equipped with two O-rings 122 and 124 is inserted into a second pin hole 118 formed in the cell body 64. The battery sample and the two pins 74 and 78 are electrically connected via two connecting members 116 and 128.

Description

Technical Field

[0001] The present invention relates to a cell for NMR measurement and an NMR measurement probe including the same, and particularly relates to NMR measurement of a battery sample that undergoes charge and discharge.

Background Art

[0002] Various secondary batteries (charge-discharge type batteries, hereinafter simply referred to as batteries), such as lithium ion batteries, are being utilized. Recently, the development of solid batteries having a solid electrolyte has been underway.

[0003] Various measuring devices are used to evaluate the performance and behavior of batteries. Among them, there is an NMR (Nuclear Magnetic Resonance) measuring device. For example, in a probe of an NMR measuring device, a laminate corresponding to a part of a battery is arranged. The laminate can be referred to as a battery sample. While the charge and discharge of the battery sample are repeated, the NMR generated in the battery sample is measured. The realization of a highly practical battery sample container (cell for NMR measurement) for such In-Situ measurement is desired.

[0004] The NMR measuring device described in Patent Document 1 includes a cavity for accommodating a sample and a mechanism for changing the angle of the cavity. The NMR measuring device described in Patent Document 2 includes a mechanism for rotating a sample chamber. Patent Documents 1 and 2 do not disclose equipment for measuring NMR generated in a battery during the charge and discharge process of the battery.

[0005] The NMR measuring device described in Patent Document 3 includes an assembly including a battery sample. The battery sample includes two conductors drawn from the inside to the outside of the assembly. The exchange of the two conductors cannot be performed or the exchange of the two conductors is extremely difficult. Patent Document 4 describes a technique for measuring NMR generated in a battery sample.

[0006] Patent documents 1 to 4 do not disclose easily replaceable conductors used in the charging and discharging of battery samples, nor do they disclose sealing structures for such conductors. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] U.S. Patent No. 6,538,444 [Patent Document 2] U.S. Patent No. 9,194,920 [Patent Document 3] U.S. Patent No. 10,126,366 [Patent Document 4] U.S. Patent No. 11,215,686 [Overview of the project] [Problems that the invention aims to solve]

[0008] An NMR measurement cell is provided with a sealed containment space inside. When measuring the NMR generated by a battery sample while repeatedly charging and discharging the battery sample, it is necessary to provide two conductors that span both the inside and outside of the cell. If the two conductors are integrated with the battery sample, it becomes difficult to replace only the two conductors. Even if the two conductors are separate from the battery sample, if adhesive is introduced into the gap between the cell body and the two conductors to seal it, it becomes difficult to replace the two conductors, similar to the above. In that case, it also becomes difficult to reuse the cell body. During testing and measurement of battery samples, the conductors are prone to contamination and corrosion. To address conductor degradation, it is desirable to be able to easily replace the conductors while ensuring the airtightness of the containment space.

[0009] The object of the present invention is to provide a replaceable charge / discharge conductor in an NMR measurement cell while ensuring internal airtightness. Alternatively, the object of the present invention is to provide an NMR measurement probe that can change the orientation of the NMR measurement cell. [Means for solving the problem]

[0010] The NMR measurement cell according to the present invention is characterized by comprising: a cell body having a housing space for housing a battery sample having a first electrode layer and a second electrode layer; a first pin inserted into a first pin hole of the cell body and electrically connected to the first electrode layer for charging and discharging the battery sample; a second pin inserted into a second pin hole of the cell body and electrically connected to the second electrode layer for charging and discharging the battery sample; a first elastic member that seals the space between the first pin hole and the first pin while allowing insertion and removal movement of the first pin; and a second elastic member that seals the space between the second pin hole and the second pin while allowing insertion and removal movement of the second pin.

[0011] The NMR measurement probe according to the present invention comprises an NMR measurement cell, a holder for holding the NMR measurement cell, and an NMR measurement coil provided around the NMR measurement cell, wherein the NMR measurement cell has a central axis, and the holder holds the NMR measurement cell so that the rotation angle of the NMR measurement cell can be changed around the central axis, and has a locking mechanism for locking the rotation angle. [Effects of the Invention]

[0012] According to the present invention, in an NMR measurement cell, the conductors for charging and discharging can be replaced while ensuring airtightness inside the cell. Alternatively, according to the present invention, an NMR measurement probe can be provided that allows the orientation of the NMR measurement cell to be changed. [Brief explanation of the drawing]

[0013] [Figure 1] This figure shows a probe for NMR measurement according to an embodiment. [Figure 2] This is a front view showing the retainer. [Figure 3] This is a cross-sectional view showing the retainer. [Figure 4] This is a front view showing the measurement unit. [Figure 5] It is a perspective view showing a cell. [Figure 6] It is a side view showing a cell. [Figure 7] It is a cross-sectional view showing a cell. [Figure 8] It is a view showing the first sub-assembly and the second sub-assembly. [Figure 9] It is a view showing a battery sample, a first connection member, and a second connection member. [Figure 10] It is a view showing the flow of the temperature-variable gas. [Figure 11] It is a flowchart showing the measurement method according to the embodiment. [Figure 12] It is a view showing a cell for NMR measurement according to another embodiment.

Embodiments for Carrying Out the Invention

[0014] Hereinafter, embodiments will be described based on the drawings.

[0015] (1) Outline of the Embodiment The cell for NMR measurement according to the embodiment has a cell body, a first pin, a second pin, a first elastic member, and a second elastic member. The cell body includes an accommodation space for accommodating a battery sample having a first electrode layer and a second electrode layer. The first pin is inserted into a first pin hole of the cell body for charging and discharging the battery sample and is electrically connected to the first electrode layer. The second pin is inserted into a second pin hole of the cell body for charging and discharging the battery sample and is electrically connected to the second electrode layer. The first elastic member seals between the first pin hole and the first pin while allowing the insertion and extraction movement of the first pin. The second elastic member seals between the second pin hole and the second pin while allowing the insertion and extraction movement of the second pin.

[0016] According to the above configuration, since a first elastic member is provided between the first pin and the first pin hole, the first pin can be easily replaced, and the airtightness of the housing space can be ensured after the first pin is replaced. Similarly, since a second elastic member is provided between the second pin and the second pin hole, the second pin can be easily replaced, and the airtightness of the housing space can be ensured after the first pin is replaced. For example, a deteriorated pin can be replaced with a new pin, or a pin made of one material can be replaced with a pin made of another material.

[0017] A battery sample corresponds to an electrochemical device. A battery sample typically has multiple layers stacked together. These layers include a positive electrode layer and a negative electrode layer. For example, the first electrode layer is a conductive layer bonded to the positive electrode layer or the positive electrode layer itself. The second electrode layer is a conductive layer bonded to the negative electrode layer or the negative electrode layer itself.

[0018] In this embodiment, the first pin is made of a first material of the same type as the material constituting the first electrode layer. The second pin is made of a second material of the same type as the material constituting the second electrode layer, but different from the first material. This configuration can prevent or reduce galvanic corrosion (collision between dissimilar metals) that occurs in corrosive environments. The pin may be made of the same material as the electrode layer material, or it may be made of a material equivalent to the electrode layer material. Generally, a relationship between identical materials is recognized when the main components of the electrode layer material and the main components of the pin constituent material are the same. In batteries, the materials constituting the first electrode layer and the materials constituting the second electrode layer are usually different.

[0019] The NMR measurement cell according to this embodiment has a pin series consisting of multiple pins made of multiple different materials. The first and second pins are selected from the pin series. Multiple pin series consisting of multiple pins made of various materials are prepared, and two pins to be used are selected according to the battery sample to be measured, specifically according to the material of the first electrode layer and the material of the second electrode layer. Multiple pins constituting the pin series have the same shape. Multiple pins having different shapes may be prepared.

[0020] The NMR measurement cell according to this embodiment has a first connecting member and a second connecting member. The first connecting member is made of a first material and electrically connects a first pin and a first electrode layer. The second connecting member is made of a second material and electrically connects a second pin and a second electrode layer. With this configuration, as described above, it is possible to prevent or reduce galvanic corrosion.

[0021] In this embodiment, the first connecting member has an end that physically contacts and elastically deforms with the first electrode layer. The second connecting member has an end that physically contacts and elastically deforms with the second electrode layer. This configuration reduces the contact resistance between the first electrode layer and the first connecting member, and between the second electrode layer and the second connecting member. Each end may be processed to resemble a spring or an elastic piece. Each connecting member may be compositionally deformed, thereby adjusting the position of each end.

[0022] In this embodiment, the first elastic member is a plurality of elastic rings arranged in the axial direction of the first pin. The second elastic member is a plurality of elastic rings arranged in the axial direction of the second pin. With this configuration, the gap between the first pin hole and the first pin can be reliably sealed, and the gap between the second pin hole and the second pin can also be reliably sealed. When gas is generated in the battery sample during charging and discharging, the gas will not be unintentionally leaked to the outside.

[0023] In this embodiment, the cell body is composed of a first part and a second part. A housing space is formed when the first part and the second part are joined together. The first pin hole is formed in the first part, and the second pin hole is formed in the second part. This configuration avoids complicating the structure of either the first part or the second part. As a result, the thickness of the first part and the second part can be reduced.

[0024] In this embodiment, the orientation of the first pin hole and the orientation of the second pin hole are opposite. This configuration allows for a distance between the position where the first signal line is connected to the first pin and the position where the second signal line is connected to the second pin, resulting in improved workability. Furthermore, it reduces the likelihood of accidental short circuits between signal lines.

[0025] In this embodiment, at least one of the first and second portions has a passage leading to a containment space. The gas generated in the battery sample is extracted through the passage. A gas chromatograph may be connected to the passage via a tube. A mass spectrometer may be connected to the gas chromatograph.

[0026] In this embodiment, the cell body has a width direction (x), a central axis direction (y), and a thickness direction (z). The cell body has a first end, an intermediate part, and a second end aligned in the y direction. In the z direction, the thickness of the intermediate part is smaller than the thickness of the first end and the second end. With this configuration, when the temperature of the battery sample is varied by blowing a temperature-variable gas onto the cell, heat conduction to the battery sample is improved. The temperature of the battery sample may be varied by other methods.

[0027] In this embodiment, the containment space extends in the x and y directions and has a first inner surface and a second inner surface that intersect in the z direction. The intermediate portion has a first exposed surface extending along the first inner surface and a second exposed surface extending along the second inner surface. The first exposed surface is the first outer surface, and the second exposed surface is the second outer surface. A temperature-variable gas is in contact with the first and second exposed surfaces.

[0028] The NMR measurement probe according to this embodiment includes the above-described NMR measurement cell, holder, and NMR measurement coil. The holder holds the NMR measurement cell. The NMR measurement coil is provided around the NMR measurement cell. The NMR measurement cell has a central axis. The holder holds the NMR measurement cell so that the rotation angle of the NMR measurement cell around the central axis can be changed. The holder also has a locking mechanism for locking the rotation angle.

[0029] This configuration allows the orientation of the battery sample to be changed with respect to a static magnetic field. For example, the rotation angle of the battery sample can be changed according to the crystal orientation of a specific substance in the battery sample. Alternatively, the rotation angle of the battery sample can be changed to investigate that crystal orientation. The rotation angle of the battery sample can be changed in steps or continuously. Two mutually orthogonal rotation axes may be provided.

[0030] In one embodiment, the locking mechanism includes a plurality of grooves provided in one of the cell body and the retainer, and a locking pin provided in the other of the cell body and the retainer, which is inserted into a specific groove selected from among the plurality of grooves. This configuration allows for easy locking of the rotation angle. The mechanism for changing and locking the rotation angle of the battery sample may also be called a goniometer mechanism.

[0031] (2) Details of the embodiment Figure 1 shows a part of an NMR measurement system for measuring a battery sample during the charging and discharging process. The NMR measurement system has an NMR measurement probe (hereinafter simply referred to as "probe") 10 according to this embodiment. The battery sample corresponds to, for example, a part of a lithium-ion battery or a solid-state battery.

[0032] The NMR measurement system further includes a spectrometer (not shown), a static magnetic field generator 16, a charge / discharge device 30, a gas analyzer (not shown), etc. The spectrometer includes a transmitter, a receiver, a spectrum generation unit, etc. The static magnetic field generator 16 is composed of a superconducting magnet. The charge / discharge device 30 is used for charging and discharging the battery sample. In this embodiment, the NMR generated in the battery sample is measured while repeatedly charging and discharging the battery sample.

[0033] The gas analyzer consists of, for example, a gas chromatograph, or a gas chromatograph followed by a mass spectrometer. The gas analyzer analyzes the gases generated in the battery sample during the charging and discharging process. If necessary, a temperature-adjustable gas supply system is provided to bring the battery sample to a desired temperature.

[0034] In Figure 1, the X direction is the first horizontal direction, and the Z direction is the vertical direction. The Y direction, which is the second horizontal direction, is not shown in Figure 1. The Z direction is the direction of the static magnetic field. The X, Y, and Z directions are orthogonal to each other.

[0035] The probe 10 consists of an insertion part 12 and a base part 14. The insertion part 12 is inserted into the bore 18 of the static magnetic field generator 16. The base part 14 is positioned outside the static magnetic field generator 16. The base part 14 and the spectrometer are connected via a cable. The base part 14 is also connected to the charge / discharge device 30 via a cable. The insertion part 12 has a cylindrical part 20 and a measuring unit 24. The cylindrical part 20 has an upper surface 22 that functions as a base, and the measuring unit 24 is fixed to the upper surface 22.

[0036] The measurement unit 24 includes a holder 26 and an NMR measurement cell (hereinafter simply referred to as "cell") 28. The cell 28 is a container for housing an electron sample. The cell 28 has a central axis. In Figure 1, the central axis is parallel to the Y direction.

[0037] The retainer 26 holds the cell 28 so that it can rotate around its central axis. The retainer 26 has a locking mechanism for locking the rotation angle of the cell 28, as will be described later. The cell 28 is positioned so that its central axis coincides with the central axis of the coil, which will be described later.

[0038] Figure 2 shows a retainer 26. The retainer 26 has a retainer body 32 and legs 34. The legs 34 support the retainer body 32. The base 34A of the legs 34 is fixed to the cylindrical part. A wedge-shaped gap exists between the base 34A and the retainer body 32. A coil for NMR measurement is incorporated into the retainer 26. In Figure 2, a pair of legs 60A and 60B of the coil are shown. Electrical components such as capacitors may be placed in the wedge-shaped gap. A terminal block to which a first signal line and a second signal line are connected may be provided to the base 34A.

[0039] The retainer 26 has a cylindrical measuring space 46 that extends in the Y direction. The cell is placed in the measuring space 46. The retainer body 32 has an opening edge 40 that surrounds the opening 38. As will be described later, the opening edge 40 holds the large diameter portion at the first end of the cell body. The opening 44 is circular when viewed from the Y direction. However, since the Y-direction end of the retainer body 32 is rounded when viewed from the Z direction, in Figure 2 the opening 44 is represented by a loop containing two straight lines. Reference numeral 42 indicates an opening edge that is located further back than the opening edge 40. The opening edge 42 surrounds the opening 44. The opening edge 42 holds the small diameter portion at the first end of the cell body.

[0040] The lock pin 48 is a component for fixing the rotation angle of the cell. The axial direction of the lock pin is parallel to the Y direction. Reference numeral 50 indicates a connector for introducing a temperature-variable gas. The III-III cross section shown in Figure 2 is shown in Figure 3. The retainer 26 is made of a non-magnetic material, specifically PEEK (Poly Ether Ether Ketone). The retainer 26 may be made of ceramic, glass, or the like.

[0041] In Figure 3, a coil 60 is incorporated inside the retainer 26. The coil 60 has a coil body 60C that surrounds the measurement space 46. The coil 60 also has a pair of legs 60A and 60B connected to the coil body 60C. The cell is arranged non-contact within the coil body 60C. The central axis of the coil 60 is parallel to the Z direction, and the central axis of the coil 60 and the central axis (rotation axis) of the cell coincide. A well-shaped gas discharge passage 58 is formed in the retainer body 32. The gas discharge passage 58 is connected to the measurement space 46. Reference numeral 58A indicates the outlet of the gas discharge passage 58.

[0042] The first end of the retainer body 32 is fitted into the openings 38 and 44, and the first end is held by the opening edges 40 and 42. Specifically, as will be described later, the first end has a large diameter portion and a small diameter portion. The large diameter portion is fitted into the opening 38, and the small diameter portion is fitted into the opening 44. The second end of the retainer body 32 is fitted into the opening 54, and the second end is held by the opening edge 56.

[0043] Figure 4 shows the measuring unit 24. The cell 28 is held by the retainer 26. In Figure 4, the rotation angle of the cell 28 is 0 degrees. The rotation angle of the cell 28 can be selected from 0 degrees, 30 degrees, 60 degrees, and 90 degrees. The cell 28 has a groove row 63 consisting of four grooves corresponding to the four rotation angles.

[0044] The locking mechanism 62 is a mechanism that spans the retainer 26 and the cell 28. However, it may also be understood that the locking mechanism 62 is provided on the retainer 26. The locking mechanism 62 consists of a row of grooves 63 and a locking pin 48. The locking pin 48 is actually a screw. Each groove constituting the row of grooves 63 has a semicircular shape when viewed from the Y direction. One groove is formed in the retainer body. This groove also has a semicircular shape when viewed from the Y direction. The combination of the two grooves forms a circular hole into which the locking pin 48 is inserted.

[0045] A series of grooves may be formed on the retainer body 32 side, and a locking pin may be provided on the cell 28 side. In this embodiment, the rotation angle of the cell is switched in steps, but the rotation angle may be switched continuously. One end of the first signal line 204 is connected to the first pin of the cell 28. The other end of the first signal line is connected to a terminal block 208 fixed to the base 34A. One end of the second signal line 206 is connected to the second pin of the cell 28. The other end of the second signal line is connected to the terminal block 208.

[0046] Figure 5 shows cell 28. The width direction is the x-direction, the central axis direction is the y-direction, and the thickness direction is the z-direction. The x, y, and z directions are orthogonal to each other.

[0047] Cell 28 includes a cell body 64, a first pin 74, a second pin 78, etc. The cell body 64 has a first end portion 68, an intermediate portion 66, and a second end portion 70 arranged in the y direction. The first end portion 68 has a small diameter portion 71 and a large diameter portion 72. In the xz plane, the diameter of the large diameter portion 72 is larger than the diameter of the small diameter portion 71. The above-mentioned row of grooves 63 is formed in the large diameter portion 72.

[0048] The second end portion 70 has the same diameter in the xz plane as the small-diameter portion 71 of the first end portion 68. The first end portion 68 also has an outlet 85 for releasing gas generated in the battery sample. The outlet 85 is connected to a gas analyzer via a tube (not shown). When gas analysis is not performed, the outlet 85 is sealed by a sealing member.

[0049] From a different perspective, cell 28 consists of a first subassembly 82 and a second subassembly 84 aligned in the z direction. In Figure 5, the first subassembly 82 corresponds to the upper part, and the second subassembly 84 corresponds to the lower part. The combination of the first subassembly 82 and the second subassembly 84 forms a housing space within cell 28. This housing space is a sealed space, and the battery sample is placed in this housing space.

[0050] The first subassembly 82 has a first pin 74. The second subassembly 84 has a second pin 78. A first nut 76 is attached to the base end of the first pin 74. A second nut 80 is attached to the base end of the second pin. The first nut 76 and the second nut 80 are components for fixing signal wires. By tightening the first nut 76, a first signal wire (not shown) for charging and discharging is attached to the first pin 74. By tightening the second nut 80, a second signal wire (not shown) for charging and discharging is attached to the second pin 78.

[0051] Notches (recesses) 65A and 65B are formed on both sides of the intermediate portion 66 in the z direction. As a result, in the z direction, the thickness of the intermediate portion 66 is smaller than the thickness of the first end portion 68 and the thickness of the second end portion 70.

[0052] Figure 6 shows a side view of the cell. Focusing on the z-direction, the cell is broadly composed of a first subassembly 82 and a second subassembly 84. Focusing on the y-direction, the cell body 64 consists of a first end 68, an intermediate section 66, and a second end 70. At the first end 68, the large-diameter section 72 consists of a portion 72A belonging to the second subassembly 84 and a portion 72B belonging to the first subassembly 82.

[0053] The first subassembly 82 has a first pin. A first nut 76 is attached to the base end 74A of the first pin. The first subassembly 82 has a first projection 94 that holds the base end 74A. The second subassembly 84 has a second pin. A second nut is attached to the base end 78A of the second pin. The second subassembly 84 has a second projection 96 that holds the base end 78A. The first subassembly 82 and the second subassembly 84 are fastened together by a plurality of screws 92.

[0054] In the z-direction, the thickness W1 of the intermediate portion 66 is smaller than the thickness W2 of the first end portion 68 (specifically the small diameter portion 71) and also smaller than the thickness W3 of the second end portion 70. The intermediate portion 66 has a first exposed surface 66a facing the positive z-direction and a second exposed surface 66b facing the negative z-direction. A housing space for housing a battery sample is provided between the first exposed surface 66a and the second exposed surface 66b. By bringing the first exposed surface 66a and the second exposed surface 66b closer to the housing space, thermal conductivity can be improved.

[0055] Figure 7 shows a cross-section (yz section) of the cell. As described above, the cell is composed of a first subassembly 82 and a second subassembly 84. The cell body 64 consists of a first part 64A belonging to the first subassembly 82 and a second part 64B belonging to the second subassembly 84. The first part 64A has a joint surface 100, and the second part 64B has a joint surface 101. The first subassembly 82 and the second subassembly 84 are joined together such that the joint surface 100 and the joint surface 101 are joined to each other.

[0056] The cell has a housing space 104 for housing a battery sample. The housing space 104 consists of a first part 104A belonging to the first subassembly 82 and a second part 104B belonging to the second subassembly 84. The second part 104B has a groove 102 surrounding the second part 104B in the housing space 104. An O-ring 103, which is an elastic sealing member, is placed in the groove 102. When the first subassembly 82 and the second subassembly 84 are fastened together, the O-ring 103 is compressed, thereby making the housing space 104 a sealed space, or airtight space.

[0057] The first portion 64A has a first pin hole 106 formed from the first end 68 to the intermediate portion 66. The first pin hole 106 communicates with the housing space 104 via a connecting passage 106a. A first pin 74 is inserted into the first pin hole 106. The first pin 74 has a base end 74A, to which a first nut 76 is attached. The first pin 74 also has a tip end 74B. The tip end 74B has a hole 114 parallel to the y-direction.

[0058] The first pin 74 has two grooves aligned in the y-direction, and two O-rings 110 and 112 are positioned in these grooves. Each of the two O-rings 110 and 112 is made of an elastic material, and the whole unit functions as a sealing member. That is, the gap between the first pin hole 106 and the first pin 74 is sealed by the two O-rings 110 and 112.

[0059] The first pin 74 is removable. A male thread formed on the outer surface of the first sleeve 108 engages with a female thread formed on the inner surface of the first projection. This fixes the first pin 74 to the first pin hole 106. By removing the first sleeve 108, the first pin 74 can be easily pulled out of the first pin hole 106.

[0060] The second portion 64B has a second pin hole 118 formed from the second end 70 to the intermediate portion 66. The second pin hole 118 communicates with the housing space 104 via a connecting passage 118a. A second pin 78 is inserted into the second pin hole 118. The second pin 78 has a base end 78A to which a second nut 80 is attached. The second pin 78 also has a tip end 78B. The tip end 78B has a hole 126 parallel to the y-direction.

[0061] The second pin 78 has two grooves aligned in the y-direction, and two O-rings 122 and 124 are positioned in these grooves. Each of the two O-rings 122 and 124 is made of an elastic material, and the whole together functions as a sealing member. That is, the gap between the second pin hole 118 and the second pin 78 is sealed by the two O-rings 122 and 124.

[0062] The second pin 78 is removable. A male thread formed on the outer surface of the second sleeve 120 engages with a female thread formed on the inner surface of the second projection. This fixes the second pin 78 in the second pin hole 118. By removing the second sleeve 120, the second pin 78 can be easily pulled out of the second pin hole 118.

[0063] A first connecting member 116 is provided in the space from the first portion 104A to the first pin hole 106 in the housing space 104. The first connecting member 116 has a first base end 116a, a first tip end 116b, and a first intermediate portion 116c. The first base end 116a is inserted into the hole 114 and is crimped and fixed in that state. The first tip end 116b is an elastically deformable portion and has a helical coil or spring shape. The elastic deformation of the first tip end 116b enhances the physical contact between the first tip end 116b and the battery sample, thereby reducing contact resistance. Note that in Figure 7, the shape of the first tip end 116b is represented as flat.

[0064] A second connecting member 128 is provided in the space from the second portion 104B to the second pin hole 118 in the housing space 104. The second connecting member 128 has a second base end 128a, a second tip end 128b, and a second intermediate portion 128c. The second base end 128a is inserted into the hole 126 and is crimped and fixed in that state. The second tip end 128b is an elastically deformable portion and has a helical coil or spring-like shape. The elastic deformation of the second tip end 128b enhances the physical contact between the second tip end 128b and the battery sample, thereby reducing contact resistance. Note that in Figure 7, the shape of the second tip end 128b is represented as flat.

[0065] The battery sample has a first electrode layer made of a first material (first conductive material) and a second electrode layer made of a second material (second conductive material). The materials constituting the first pin 74 and the first connecting member 116 are the same type of material as the first material, and in practice, are the same material as the first material. The first material is, for example, aluminum. By making the multiple members arranged in the first subassembly 82 from the same type of material in this way, galvanic metal contact corrosion in a corrosive environment can be prevented or reduced. In this embodiment, the materials constituting the first nut 76 and the first sleeve 108 are also the same type of material as the first material, and in practice, are the same material as the first material. The first nut may be made of a different material from the first material, for example, an insulating material such as engineering plastic. Examples of engineering plastics include PEEK and VESPEL.

[0066] The materials constituting the second pin 78 and the second connecting member 128 are of the same type as the second material, and in fact, they are the same material as the second material. The second material is, for example, copper. By constituting multiple members arranged within the second subassembly 84 with the same type of material in this way, galvanic metal contact corrosion in a corrosive environment can be prevented or reduced. In this embodiment, the materials constituting the second nut 80 and the second sleeve 120 are also of the same type as the second material, and in fact, they are the same material as the second material. The second nut may be made of a different material from the second material, for example, an insulating material such as engineering plastic.

[0067] The second portion 64B of the cell body 64 has a gas discharge passage 129. The gas discharge passage 129 communicates with the containment space 104 via a passage 118a. The gas discharge passage 129 has an outlet 85. The cell body 64 is made of a non-magnetic and insulating material, such as PEEK. The cell body 64 may also be made of ceramic, glass, or the like.

[0068] Multiple pins of the same shape made from multiple different materials may be prepared as a pin series, and two pins to be used may be selected from the pin series according to the materials constituting the first electrode layer and the materials constituting the second electrode layer. In this case, a series of connecting members, a series of nuts, and a series of sleeves may also be prepared.

[0069] Figure 8 shows the first subassembly 82 and the second subassembly 84. The first subassembly 82 is inverted. The first subassembly 82 has a first portion 104A as a recess, in which the first tip of the first connecting member 116 is positioned. Reference numeral 130 indicates the ceiling surface as the first inner surface.

[0070] The second subassembly 84 has a second portion 104B as a recess, in which the second tip of the second connecting member 128 is positioned. Reference numeral 132 indicates the bottom surface as the second inner surface. An annular groove is formed around the second portion 104B, and the O-ring 103 is positioned in the groove.

[0071] Figure 9 shows the battery sample 200 arranged in the containment space. The battery sample 200 is a laminate. The battery sample 200 has, for example, a rectangular or circular shape when viewed from the z direction. The battery sample 200 has, for example, a width of 7 to 12 mm and a thickness of 1 to 3 mm.

[0072] The battery sample 200 has a first electrode layer and a second electrode layer. The tip portion 116b of the first connecting member 116 is in contact with the first electrode layer. The tip portion 128b of the second connecting member 128 is in contact with the second electrode layer.

[0073] If the thickness of the battery sample 200 is small, a spacer 202 is placed between the tip 128b and the bottom surface. The spacer 202 is provided with an opening or notch for the passage of the second connecting member. A spacer may also be placed between the tip 116b and the top surface. Multiple spacers with different thicknesses may be prepared as a spacer series, and the spacer to be used may be selected from the spacer series.

[0074] Figure 10 shows the flow of a temperature-variable gas. The cell 28 and coil 60 are positioned within the measurement space. The user can select any rotation angle for the cell 28. The gas introduced into the retainer 26 through the gas introduction passage 134 is released into the measurement space. The gas flows around the cell 28, enveloping it, and is then discharged to the outside through the gas discharge passage 58. As the gas flows, it comes into contact with the surface of the cell 28, particularly the first exposed surface 66a and the second exposed surface 66b, which are close to the containment space. This results in heat exchange between the cell 28 and the gas. Reference numerals 136A and 136B indicate heat conduction within the cell 28. The temperature-variable range is, for example, -100°C to +100°C.

[0075] In this embodiment, since the first exposed surface 66a and the second exposed surface 66b are close to the containment space, good heat conduction can be achieved between the battery sample and the gas, and in particular, the temperature of the battery sample can be adjusted quickly. The temperature of the battery sample may be varied by irradiating the cell with laser light. A heat source may be connected to the cell via a heat conductive member, thereby varying the temperature of the battery sample inside the cell.

[0076] Figure 11 shows a flowchart illustrating the measurement method according to the embodiment. In S10, a first pin and a second pin are selected from the pin series. Specifically, a first pin made of the same material as the first material constituting the first electrode layer in the battery sample is selected, and a second pin made of the same material as the second material constituting the second electrode layer in the battery sample is selected. Similarly, a first connecting member and a second connecting member are selected from the connecting member series, a first nut and a second nut are selected from the nut series, and a first sleeve and a second sleeve are selected from the sleeve series.

[0077] In S12, the first base end of the first connecting member is attached to the tip of the first pin. A crimping method is used for this. The first connecting member may be inserted into the first pin hole prior to its attachment, or it may be inserted into the first pin hole after its attachment. Also in S12, the second base end of the second connecting member is attached to the tip of the second pin. A crimping method is used for this. The second connecting member may be inserted into the second pin hole prior to its attachment, or it may be inserted into the second pin hole after its attachment.

[0078] In S14, the first pin is inserted into the first pin hole, and the first pin is attached to the cell body. A first sleeve is used for this purpose. The first connecting member has a first tip. For example, the first tip is processed to resemble a helical coil. The first tip is the part that is positioned in the first part of the housing space. Also in S14, the second pin is inserted into the second pin hole in the cell body, and the second pin is attached to the cell body. A second sleeve is used for this purpose. The second connecting member has a second tip. For example, the second tip is processed to resemble a helical coil. The second tip is the part that is positioned in the second part of the housing space. After the first pin is attached, the first signal wire is connected to the base end of the first pin. A first nut is used for this purpose. After the second pin is attached, the second signal wire is connected to the base end of the second pin. A second nut is used for this purpose. Procedures different from the above procedure may be adopted.

[0079] In S16, the battery sample is placed in the containment space. In S18, the first and second parts that make up the cell are joined together, thereby assembling the cell. In S20, the cell is fixed to the holder. At this time, a desired rotation angle is selected.

[0080] In S22, a probe equipped with a holder is positioned relative to the static magnetic field generator. In S24, the NMR generated in the battery sample is measured. Subsequently, if necessary, the rotation angle of the cell is changed, and the NMR generated in the battery sample is measured again.

[0081] Figure 12 shows a portion of a probe according to another embodiment. The Z direction indicates the direction of the static magnetic field. A saddle-type coil 146 is placed in the measurement space. The internal space of the coil 146 has a cylindrical shape. A cell 140 is placed in its internal space. The cell 140 is composed of a first subassembly 142 and a second subassembly 144. In Figure 12, the cell 140 is shown schematically. The cell 140 basically has the same shape and structure as the cell shown in Figures 6 to 8. However, the orientation of the cell 140 is different from the orientation of the cell shown in Figures 6 to 8.

[0082] According to the cell of the above embodiment, since the pins are arranged to be insertable and removable from the cell body, it becomes easy to replace the pins while ensuring the airtightness of the containment space. For example, a deteriorated pin can be replaced with a new pin, or a pin made of one material can be replaced with a pin made of another material. By replacing the pins, the cell body can be reused.

[0083] In the above embodiment, the orientation of the first pin and the second pin were reversed, but their orientations may be the same. Reversing the two orientations has the advantage of improving workability. It also prevents unintentional short circuits. In the above embodiment, the entire cell had a cylindrical shape, but the entire cell may have a flat plate shape or a block shape. In the above embodiment, an electrochemical device other than a general secondary battery may be measured as an electronic sample. [Explanation of symbols]

[0084] 10 NMR measurement probe, 24 measurement unit, 26 holder, 28 NMR measurement cell, 60 coil, 62 locking mechanism, 64 cell body, 66 intermediate section, 68 first end, 70 second end, 74 first pin, 78 second pin, 106 first pin hole, 110, 112 O-rings, 116 first connecting member, 118 second pin hole, 122, 124 O-rings, 128 second connecting member.

Claims

1. A cell body having a storage space for housing a battery sample having a first electrode layer and a second electrode layer, For charging and discharging the battery sample, a first pin is inserted into a first pin hole in the cell body and electrically connected to the first electrode layer, For charging and discharging the aforementioned battery sample, a second pin is inserted into a second pin hole in the cell body and electrically connected to the second electrode layer, A first elastic member that seals the space between the first pin hole and the first pin while allowing the insertion and removal movement of the first pin, A second elastic member that seals the space between the second pin hole and the second pin while allowing the insertion and removal movement of the second pin, An NMR measurement cell characterized by containing [a specific component].

2. In the NMR measurement cell according to claim 1, The first pin is made of the same first material as the material constituting the first electrode layer, The second pin is made of a second material of the same type as the material constituting the second electrode layer, but different from the first material. An NMR measurement cell characterized by the following features.

3. In the NMR measurement cell according to claim 1, A first connecting member that electrically connects the first pin and the first electrode layer, A second connecting member that electrically connects the second pin and the second electrode layer, An NMR measurement cell characterized by containing [a specific component].

4. In the NMR measurement cell according to claim 3, The first connecting member has an end that physically contacts the first electrode layer and undergoes elastic deformation, The second connecting member has an end that physically contacts the second electrode layer and undergoes elastic deformation, An NMR measurement cell characterized by the following features.

5. In the NMR measurement cell according to claim 1, The first elastic member is a plurality of elastic rings arranged in the axial direction of the first pin, The second elastic member is a plurality of elastic rings arranged in the axial direction of the second pin. An NMR measurement cell characterized by the following features.

6. In the NMR measurement cell according to claim 1, The cell body is composed of a first part and a second part, The housing space is formed in the state in which the first part and the second part are joined together. The first pin hole is formed in the first portion, The second pin hole is formed in the second portion. An NMR measurement cell characterized by the following features.

7. In the NMR measurement cell according to claim 6, The orientation of the first pin hole and the orientation of the second pin hole are opposite. An NMR measurement cell characterized by the following features.

8. In the NMR measurement cell according to claim 6, At least one of the first and second portions has a passage leading to the accommodation space, The gas generated in the battery sample is removed through the passage. An NMR measurement cell characterized by the following features.

9. In the NMR measurement cell according to claim 1, The cell body has a width direction (x), a central axis direction (y), and a thickness direction (z). The cell body has a first end, an intermediate part, and a second end, which are aligned in the y direction. In the z-direction, the thickness of the intermediate portion is smaller than the thickness of the first end and the thickness of the second end. An NMR measurement cell characterized by the following features.

10. In the NMR measurement cell according to claim 9, The aforementioned accommodation space extends in the x-direction and the y-direction and has a first inner surface and a second inner surface that intersect in the z-direction. The intermediate portion has a first exposed surface extending along the first inner surface and a second exposed surface extending along the second inner surface. An NMR measurement cell characterized by the following features.

11. The NMR measurement cell according to claim 1, A holder for holding the NMR measurement cell, An NMR measuring coil provided around the aforementioned NMR measuring cell, Includes, The NMR measurement cell has a central axis, The holder holds the NMR measuring cell so that the rotation angle of the NMR measuring cell around the central axis can be changed. The retainer has a locking mechanism for locking the rotation angle. A probe for NMR measurement characterized by the following features.

12. In the NMR measurement probe according to claim 11, The locking mechanism is The cell body and the retainer have a plurality of grooves provided in one of them, A locking pin is provided in the other part of the cell body and the retainer, and is inserted into a specific groove selected from among the plurality of grooves. A probe for NMR measurement, characterized by including [a specific component].

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