Holder, analysis device including same, and method for analyzing battery

Abstract

A holder (H) holds a battery (B) which is to be subjected to X-ray analysis. The battery (B) includes a positive electrode (B1) and a negative electrode (B2). The holder (H) is formed inside a sample chamber (R) in which the battery (B) is disposed. The holder (H) comprises a body (4), a beryllium plate (1), first resin members (2A, 2B), a conductive member (3), a positive electrode terminal (T1), and a negative electrode terminal (T2). A window (W) is formed in an upper surface of the body (4). The beryllium plate (1) is disposed at the window (W). The first resin members (2A, 2B) are each provided on a surface of the beryllium plate (1). The conductive member (3) is provided between the positive electrode (B1) and the first resin member (2B) so as to contact the positive electrode (B1) of the battery (B). The positive electrode terminal (T1) is electrically connected to the conductive member (3). The negative electrode terminal (T2) is electrically connected to the negative electrode (B2).

Description

[Technical field]

[0001] The present invention relates to a holder and an analytical device including the same, and a method for analyzing batteries, and more particularly to a battery holder for use in performing X-ray spectroscopic analysis of battery materials. [Background technology]

[0002] In the development of secondary batteries, X-ray spectroscopic analysis of battery materials is effective for investigating state changes due to charging and discharging of the battery materials that make up the battery and state changes due to deterioration. Patent Document 1 (WO 2019 / 163023) discloses an X-ray spectroscopic analysis device that disassembles a lithium-ion battery and sets the battery material to be analyzed in a sample holder for analysis. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2019 / 163023 Summary of the Invention [Problem to be solved by the invention]

[0004] Generally, secondary batteries such as lithium-ion batteries are covered with a metal case with relatively low X-ray transmittance, such as stainless steel, to protect the internal battery materials, which makes it difficult to perform X-ray measurement of the internal electrodes. Therefore, in order to perform X-ray spectroscopic analysis of battery materials, it is necessary to disassemble the battery and remove the internal battery materials. However, the method of disassembling the battery and analyzing it in this way has the first problem that the analysis is cumbersome. In addition, although it is possible to analyze the state of the battery materials at a certain point during charging and discharging, it is difficult to analyze the continuous changes in the battery materials during charging and discharging. Therefore, a means of performing X-ray spectroscopic analysis of battery materials without disassembling the battery has been long awaited.

[0005] The present disclosure has been made to solve such problems, and has an object to provide a holder that enables X-ray spectroscopic analysis of battery materials without disassembling the battery. [Means for solving the problem]

[0006] A first aspect of the present invention relates to a holder for holding a battery to be analyzed by X-ray analysis. The battery includes a positive electrode and a negative electrode. The holder has a sample chamber formed therein for placing the battery. The holder includes a body, a beryllium plate, a first resin member, a conductive member, a positive electrode terminal, and a negative electrode terminal. The body has a window formed on an upper surface. The beryllium plate is placed in the window. The first resin member is provided on a surface of the beryllium plate. The conductive member is provided between the positive electrode and the first resin member so as to contact the positive electrode of the battery. The positive electrode terminal is electrically connected to the conductive member. The negative electrode terminal is electrically connected to the negative electrode.

[0007] A second aspect of the invention relates to an analyzer for a battery. The analyzer includes a holder, a spectroscope, and a signal processor. The holder holds a battery. The spectroscope irradiates an excitation ray to the battery held in the holder, and separates the generated characteristic X-rays to detect the intensity for each wavelength. The signal processor processes a signal output from the spectroscope. The battery includes a positive electrode and a negative electrode. The holder includes a body, a beryllium plate, a resin member, a conductive member, a positive electrode terminal, and a negative electrode terminal. The body has a sample chamber formed therein for placing the battery, and a window formed in the direction of incidence of the excitation ray. The beryllium plate is placed in the window. The resin member is provided on the surface of the beryllium plate. The conductive member is provided between the positive electrode and the resin member so as to be in contact with the positive electrode. The positive electrode terminal is electrically connected to the conductive member. The negative electrode terminal is electrically connected to the negative electrode.

[0008] A third aspect of the invention is a method for analyzing a battery, comprising the steps of irradiating an excitation ray to a battery held in a holder, detecting the intensity of each wavelength by dispersing characteristic X-rays generated from the battery, and processing a signal indicating the intensity of the characteristic X-rays at each wavelength. The battery includes a positive electrode and a negative electrode. The holder includes a body, a beryllium plate, a resin member, a conductive member, a positive electrode terminal, and a negative electrode terminal. The body has a sample chamber formed therein for placing the battery, and a window formed in the direction of incidence of the excitation ray. The beryllium plate is placed in the window. The resin member is provided on the surface of the beryllium plate. The conductive member is provided between the positive electrode and the resin member so as to be in contact with the positive electrode. The positive electrode terminal is electrically connected to the conductive member. The negative electrode terminal is electrically connected to the negative electrode. Effect of the Invention

[0009] According to the present disclosure, X-ray spectroscopy of the battery can be performed by irradiating the battery material with X-rays through a beryllium plate placed in the holder window, thus allowing analysis of the battery material without dismantling the battery. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram showing a configuration of an analysis device 100 according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a diagram showing a schematic internal configuration of the device main body. [Diagram 3] FIG. 2 is a diagram showing a schematic internal configuration of the device main body. [Figure 4] FIG. [Diagram 5] FIG. 4 is a cross-sectional view showing an example of an internal configuration of a holder. [Figure 6] 4 is a cross-sectional view showing an example of a configuration in the vicinity of a window of a holder. FIG. [Figure 7] 11 is a flowchart illustrating a process related to X-ray spectroscopic analysis. [Figure 8] FIG. 11 is a cross-sectional view illustrating a first modified example of the embodiment. [Figure 9]FIG. 11 is a cross-sectional view illustrating a second modified example of the embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are designated by the same reference characters and their description will not be repeated.

[0012] [1. Configuration of the analysis device] 1 is a schematic diagram showing the configuration of an analysis apparatus 100 according to an embodiment of the present invention. Analysis apparatus 100 according to the present embodiment is an X-ray spectroscopic analysis apparatus equipped with a wavelength-dispersive spectroscope. In the following, a wavelength-dispersive X-ray fluorescence analysis apparatus will be described as an example of an X-ray spectroscopic analysis apparatus according to the present embodiment. The "wavelength-dispersive" type is a method in which characteristic X-rays are dispersed by a dispersing element, and the characteristic X-ray intensity for each target wavelength is measured to detect the characteristic X-ray spectrum.

[0013] With reference to FIG. 1, the analysis device 100 has an apparatus main body 10 and a signal processing device 20. The apparatus main body 10 is configured to irradiate a sample with excitation rays and detect characteristic X-rays generated from the sample. In the analysis device 100 according to this embodiment, the sample is a battery having a simple configuration held in a holder. The excitation rays are typically X-rays. The characteristic X-rays and fluorescent X-rays are synonymous. A detection signal corresponding to the characteristic X-rays detected by the apparatus main body 10 is transmitted to the signal processing device 20.

[0014] The signal processing device 20 includes a controller 22, a display 24, and an operation unit 26. The signal processing device 20 controls the operation of the device main body 10. The signal processing device 20 is also configured to process the detection signal transmitted from the device main body 10 and display the results based on the analysis of the signal on the display 24.

[0015] A display 24 and an operation unit 26 are connected to the controller 22. The display 24 is configured, for example, by a liquid crystal panel capable of displaying images. The operation unit 26 accepts operation inputs from a user to the analysis device 100. The operation unit 26 is typically configured by a touch panel, a keyboard, a mouse, and the like.

[0016] The controller 22 has, as its main components, a processor 30, a memory 32, a communication interface (I / F) 34, and an input / output I / F 36. These components are connected to each other via a bus so as to be able to communicate with each other.

[0017] The processor 30 is typically an arithmetic processing unit such as a CPU (Central Processing Unit) or an MPU (Micro Processing Unit). The processor 30 reads and executes a program stored in the memory 32 to control the operation of the analysis device 100. Specifically, the processor 30 executes the program to realize processing including detection of characteristic X-rays generated from the battery B and analysis of the detected characteristic X-ray data. Note that, although the example of FIG. 1 illustrates a configuration with a single processor, the controller 22 may have a configuration with multiple processors.

[0018] The memory 32 is realized by a non-volatile memory such as a random access memory (RAM), a read only memory (ROM), a flash memory, etc. The memory 32 stores programs executed by the processor 30, data used by the processor 30, etc.

[0019] The input / output I / F 36 is an interface for transmitting various types of data between the processor 30 and the display 24 and operation unit 26 .

[0020] The communication I / F 34 is a communication interface for exchanging various data with the device main body 10, and is realized by an adapter, a connector, etc. The communication method may be a wireless communication method using a wireless LAN (Local Area Network) or the like, or a wired communication method using a USB (Universal Serial Bus) or the like.

[0021] [2. Principles of wavelength dispersive X-ray analysis] 2 and 3 are diagrams showing a schematic internal configuration of the device body 10. Referring to FIG. 2 and FIG. 3, the device body 10 has a holder H holding a battery B, an excitation source 120, a slit 130, a dispersing crystal 140, and a detector 150. In FIG. 2, the surface of the holder H holding the battery B is the XY plane, and the direction of irradiation of the excitation line from the excitation source 120 is the Z-axis direction. In this specification, "up" refers to the positive direction of the Z-axis, and "down" refers to the negative direction of the Z-axis. The dispersing crystal 140 and the detector 150 constitute a "spectroscope" in this disclosure.

[0022] The excitation source 120 is an X-ray source that irradiates X-rays, which are excitation light (excitation rays), to the cell B. An electron beam source may be used as the excitation source 120 instead of an X-ray source. The excitation light emitted from the excitation source 120 is irradiated to the cell B. In the example of FIG. 2, the excitation light is irradiated perpendicularly to the surface of the cell B, but the excitation light may be irradiated at an angle inclined to the surface of the cell B.

[0023] In the analyzing crystal 140, a specific crystal plane is parallel to the crystal surface. Only the specific crystal plane can be used to detect the characteristic X-rays. This makes it possible to prevent the characteristic X-rays that are Bragg-reflected by other crystal planes from being erroneously detected.

[0024] 3, the detector 150 includes a plurality of detection elements 151. Each of the plurality of detection elements 151 extends in the Y-axis direction.

[0025] Next, the operation of the analysis device 100 according to the present embodiment will be described. As shown in FIG. 2, when the excitation source 120 irradiates the battery B with excitation rays, characteristic X-rays are emitted from the battery B. The emitted characteristic X-rays have different wavelengths depending on the material that constitutes the battery B. In FIG. 2, the excitation rays emitted from the excitation source 120 are irradiated onto a region from position A1 to position A2. The characteristic X-rays emitted from the region pass through the slit 130 and reach the analyzing crystal 140. In FIG. 2, the characteristic X-rays generated at positions A1 and A2 are exemplarily shown by dashed lines. Position A2 is a position in the positive direction of position A1 in the X-axis direction. Positions A1 and A2 each extend in the Y-axis direction (see FIG. 3).

[0026] The characteristic X-rays emitted from the cell B pass through the slit 130 and are irradiated onto the dispersing crystal 140. The angle of incidence of the characteristic X-rays on the dispersing crystal 140 varies depending on the position in the cell B where the characteristic X-rays are generated.

[0027] Of the characteristic X-rays incident on the dispersing crystal 140 from the cell B, only the characteristic X-rays having a wavelength that satisfies the condition for Bragg reflection are diffracted by the dispersing crystal 140 and reach the detector 150 .

[0028] The characteristic X-rays diffracted by the analyzing crystal 140 are emitted at the same angle as the incident angle. Therefore, the Bragg-reflected characteristic X-rays are detected by the detecting element 151 arranged at a position corresponding to the emission angle among the multiple detecting elements 151. In this way, the characteristic X-rays having wavelengths that satisfy the Bragg conditions for different diffraction angles are detected for each of the multiple detecting elements. In other words, by knowing the detecting element that detected the characteristic X-rays, it is possible to recognize the wavelength contained in the characteristic X-rays. Meanwhile, the wavelength of the characteristic X-rays differs for each substance. Therefore, by identifying the detecting element in the detector 150 that detected the characteristic X-rays, it is possible to identify the substance contained in the battery B to be analyzed.

[0029] In this way, the spectroscope of the device body 10 disperses the characteristic X-rays generated by the cell B irradiated with the excitation rays and detects the intensity for each wavelength. The device body 10 transmits the intensity for each detection element (the intensity for each of the multiple detection elements) to the signal processing device 20. This allows the signal processing device 20 to acquire multiple wavelengths and the intensities of the characteristic X-rays corresponding to each of the multiple wavelengths.

[0030] Next, calculation of the peak energy by the signal processing device 20 will be described. For energy E and wavelength λ of the characteristic X-ray, the formula E=hc / λ holds. Here, h is Planck's constant and c is the speed of light. Using this formula, the signal processing device 20 obtains the energy and the intensity of the characteristic X-ray corresponding to the energy. The signal processing device 20 measures the energy at which the intensity of the characteristic X-ray peaks (hereinafter referred to as "peak energy").

[0031] As described above, in the analysis device 100, the spectroscope of the device body 10 disperses the characteristic X-rays generated by the battery B irradiated with the excitation rays and detects the intensity for each wavelength. In addition, the signal processing device 20 processes the signal output from the device body 10. Thus, the analysis device 100 can perform X-ray spectrometry to analyze the state of the battery B.

[0032] 2, the device main body 10 may include a charging / discharging device 170. The charging / discharging device 170 is controlled by the processor 30 of the signal processing device 20. When the charging / discharging device 170 is connected to each of the positive electrode terminal T1 and the negative electrode terminal T2 of the holder H, which will be described in detail later, the charging / discharging device 170 controls the charging / discharging of the battery B. Note that the charging / discharging device 170 may be a device independent of the device main body 10 as long as it can control the charging / discharging of the battery B.

[0033] [3. Holder and battery configuration] Next, the configuration of the holder H for holding the battery B when the battery B is analyzed in the analysis device 100 will be described.

[0034] Fig. 4 is a perspective view of the holder H. Referring to Fig. 4, the holder H includes a body 4, a plate portion 12, a base plate 51, a positive terminal T1, and a negative terminal T2.

[0035] The body 4 is disposed on the base plate 51. The body 4 includes a cylindrical cell body 42 and a window body 41 disposed on the cell body 42. A sample chamber in which a battery B is disposed is formed in the body 4. A window W is formed in the window body 41 between the sample chamber and the excitation source 120. A plate portion 12 is disposed in the window W. The body 4 and the base plate 51 are preferably made of metal. For example, the body 4 and the base plate 51 are made of stainless steel.

[0036] The positive electrode terminal T1 and the negative electrode terminal T2 are each connected to a charge / discharge device 170. The battery B is charged / discharged by the charge / discharge device 170 via the positive electrode terminal T1 and the negative electrode terminal T2.

[0037] The positive electrode terminal T1 is a part that electrically connects the positive electrode of the battery B placed in the holder H to the charging / discharging device 170. In the example of FIG. 4, the positive electrode terminal T1 is a metal bar-shaped or plate-shaped terminal that is connected to the cell body 42. The positive electrode terminal T1 may be configured, for example, integrally with the cell body 42. In this way, the positive electrode terminal T1 and the cell body 42 are stably connected. In addition, for example, the positive electrode terminal T1 may be configured to be detachable from the cell body 42. In this configuration, when the battery B does not need to be connected to the charging / discharging device 170, the positive electrode terminal T1 can be detached from the cell body 42. Thus, the side of the battery B has a simple cylindrical shape. Therefore, for example, it does not get in the way when rotating the battery B. Note that the configuration of the positive electrode terminal T1 is not limited to the above example, and for example, the positive electrode terminal T1 includes a part (for example, the body 4) between the terminal that is electrically connected to the charging / discharging device 170 and detachable from the holder H and the positive electrode of the battery B.

[0038] The negative terminal T2 is a part that electrically connects the negative electrode of the battery B placed in the holder H to the charging / discharging device 170. In the example of FIG. 4, the negative terminal T2 is a metal bar-shaped or plate-shaped terminal that is connected to the base plate 51. The negative terminal T2 may be configured, for example, integrally with the base plate 51. In this way, the negative terminal T2 and the base plate 51 are stably connected. In addition, for example, the negative terminal T2 may be configured to be detachable from the base plate 51. In this configuration, when the battery B does not need to be connected to the charging / discharging device 170, the negative terminal T2 can be detached from the base plate 51. Thus, the side of the battery B has a simple cylindrical shape. Therefore, for example, it does not get in the way when the battery B is rotated. Note that the configuration of the negative terminal T2 is not limited to the above example, and for example, the negative terminal T2 includes a part (for example, the base plate 51) between the bar-shaped terminal that is electrically connected to the charging / discharging device 170 and detachable from the holder H and the negative electrode of the battery B.

[0039] 5 is a cross-sectional view showing an example of the internal configuration of the holder H and the configuration of the battery B. The holder H further includes an insulating plate 50, an insulating spacer 52, an inner cylinder 53, an electrode guide 54, a spring 55, an electrode support portion 56, and a conductive member 3.

[0040] A sample chamber R is formed inside the holder H. In the example of Fig. 5, the sample chamber R is a space surrounded by the conductive member 3, the electrode guide 54, and the electrode support portion 56. In the sample chamber R, a battery B is placed.

[0041] The battery B includes a positive electrode B1, a negative electrode B2, and a separator B3. In the example of FIG. 5, the battery B is a lithium ion secondary battery. The positive electrode B1 includes a positive electrode material B11 and a positive electrode current collector B12. The positive electrode material B11 is, for example, a single or composite metal oxide of cobalt, nickel, or manganese, or an iron phosphate-based material such as LiFePO4. The positive electrode current collector B12 is, for example, aluminum. The negative electrode B2 includes a negative electrode material B21 and a negative electrode current collector B22. The negative electrode material B21 is, for example, a carbon-based material or an alloy-based material. The negative electrode current collector B22 is, for example, copper. The separator B3 is provided between the positive electrode B1 and the negative electrode B2. The separator B3 is, for example, a microporous film made of polyolefin. The configuration, composition, and functions of each part of the lithium ion secondary battery are publicly known, so detailed description will be omitted.

[0042] The insulating plate 50 is placed under the base plate 51. The inner cylinder 53 is placed on the base plate 51 and inside the cell body 42. An electrode guide 54, an electrode support part 56, and a battery B placed in the sample chamber R are placed inside the inner cylinder 53. The insulating spacer 52 is placed between the base plate 51 and the cell body 42, and electrically insulates the base plate 51 and the cell body 42.

[0043] The insulating plate 50, the inner cylinder 53, and the insulating spacer 52 are made of an electrically insulating material, for example, polyphenylene sulfide (PPS).

[0044] The electrode guide 54 holds the spring 55. The spring 55 generates a pressing force when the electrode support part 56 is pressed from above. The electrode support part 56 is disposed on the spring 55, and transmits the pressing force of the spring 55 to the battery B. As a result, the negative electrode B2 of the battery B is in close contact with the electrode support part 56. In addition, the positive electrode B1 of the battery B is in close contact with the conductive member 3.

[0045] The electrode support portion 56 and the spring 55 are made of a conductive material. The electrode support portion 56 and the spring 55 are made of, for example, stainless steel. The electrode guide 54 is made of, for example, PPS.

[0046] With this configuration, the negative electrode B2 of the battery B is electrically connected to the negative electrode terminal T2 via the electrode support portion 56, the spring 55, and the base plate 51, as indicated by the arrow AR2.

[0047] The conductive member 3 is provided between the positive electrode B1 of battery B and the plate portion 12 so as to be in contact with the positive electrode B1 of battery B. The conductive member 3 is made of a conductive material. With this configuration, the positive electrode B1 of battery B is electrically connected to the positive terminal T1 via the conductive member 3 and the cell body 42, as indicated by the arrow AR1.

[0048] The window body 41, the plate portion 12, and the conductive member 3 function as a lid for the sample chamber R. Hereinafter, the window body 41, the plate portion 12, and the conductive member 3 will be collectively referred to as the "lid portion." The user opens this lid portion and places the battery B in the sample chamber R.

[0049] [4.Details of the battery holder window area] Fig. 6 is a cross-sectional view showing an example of the configuration in the vicinity of the window W of the holder H. Note that from Fig. 6 onwards, description of the configuration below the electrode support portion 56 is omitted.

[0050] An arrow AR3 indicates excitation rays irradiated from the excitation source 120 to the battery B. An arrow AR4 indicates characteristic X-rays generated from the battery B and detected by the spectrometer. In the example of Fig. 6, the excitation rays are irradiated to the positive electrode material B11 of the positive electrode B1 of the battery B (arrow AR3), and characteristic X-rays are generated from the positive electrode material B11 (arrow AR4).

[0051] The plate portion 12 includes resin members 2A and 2B and a beryllium plate 1. The resin members 2A and 2B correspond to one embodiment of a "first resin member."

[0052] The beryllium plate 1 has resin members 2A and 2B on the surface. Beryllium is a metal that has high X-ray permeability but may have an effect on the human body. Therefore, the resin members 2A and 2B prevent beryllium from being directly exposed to the atmosphere, allowing the user to handle the holder H without worrying too much about the effect of beryllium on the human body. For example, the user feels more secure when installing the battery B in the holder H for X-ray spectroscopic analysis. The resin members 2A and 2B are preferably made of a resin that has high X-ray permeability and is less damaged by X-rays. An example of a resin that has high X-ray permeability is a low-density resin. An example of a resin that is less damaged by X-rays is a resin with a ring structure. If the resin members 2A and 2B are configured in this way, the X-ray permeability of the resin members 2A and 2B is high. That is, as shown by the arrows AR3 and AR4, the excitation rays irradiated from the excitation source 120 and the characteristic X-rays generated from the positive electrode B1 pass through the resin members 2A and 2B. As described above, the beryllium plate 1 also has high X-ray transparency, so that the excitation rays irradiated from the excitation source 120 and the characteristic X-rays generated from the positive electrode B1 also penetrate the plate portion 12. In other words, X-ray spectroscopic analysis is possible through the plate portion 12.

[0053] Specifically, the resin members 2A and 2B are made of, for example, polyimide resin. Polyimide resin is a sturdy resin that has high X-ray transparency, excellent mechanical strength, and excellent chemical resistance. Therefore, by providing the polyimide resin on the surface, the possibility of the beryllium plate being exposed is reduced. That is, the plate portion 12 becomes easier to handle. Another example of the resin members 2A and 2B is PTFE (polytetrafluoroethylene), which is a fluororesin. Depending on the type of resin, the intensity of the irradiated excitation rays, the temperature, and the like, the moisture contained in the resin members 2A and 2B may cause a side reaction other than the battery reaction, which may adversely affect the measurement accuracy. This problem can be suppressed by using a fluororesin with high water repellency as the resin members 2A and 2B. Also, the resin members 2A and 2B may be made of different materials. For example, the upper resin member 2A, which is less likely to come into contact with the electrolyte, may be made of polyimide resin, and the lower resin member 2B may be made of fluororesin. Yet another example of the resin members 2A and 2B is PEEK (polyether ether ketone).

[0054] Moreover, it is preferable that the total thickness of the resin members 2A, 2B in the direction perpendicular to the beryllium plate 1 (Z-axis direction) is 100 μm or less. With this configuration, the X-ray transparency of the resin members 2A, 2B is sufficiently high. Even if the resin members 2A, 2B are thin, they are effective enough not to expose the beryllium, so they may be, for example, a film having a thickness of 12.5 μm, which is the thinnest among those commercially available. In other words, the thickness of the resin members 2A, 2B may be determined in consideration of the X-ray transparency and ease of handling by the manufacturer and the user.

[0055] The conductive member 3 is preferably made of aluminum. Aluminum is a metal with high X-ray transparency. On the other hand, unlike beryllium, aluminum is easy to handle because there is no concern about its effect on the human body. In addition, aluminum is highly conductive, so that the conduction between the positive electrode B1 and the positive electrode terminal T1 of the battery B is ensured. Therefore, with this configuration, the battery B can be subjected to X-ray spectroscopy analysis while being held in the holder H, and can also be charged and discharged. In addition, the conductive member 3 is easy to handle. Therefore, in this specification, unless otherwise specified, the conductive member 3 is made of aluminum.

[0056] The conductive member 3 is configured to be deposited on the resin member 2B, for example. As described later, the conductive member 3 may be a foil member, but when the conductive member 3 is deposited and integrated with the resin member 2B, it is easier for the user to handle it than when the conductive member 3 is separate from the resin member 2B. For example, there is no risk of the user accidentally dropping the conductive member 3 when putting the battery B into the sample chamber R.

[0057] Also, the conductive member 3 may be directly vapor-deposited on the underside of the beryllium plate 1. In this case, only the resin member 2A may be provided on the upper surface of the beryllium plate 1, without providing the resin member 2B. Even with this configuration, the underside of the beryllium plate 1 is not exposed, and the X-ray transparency of the window W is increased by the amount of the resin member 2B removed. On the other hand, in view of the possibility that the conductive member 3 may peel off due to repeated use, exposing the beryllium plate 1, a configuration in which the conductive member 3 is vapor-deposited on the underside of the beryllium plate 1 on which the resin member 2B has been vapor-deposited is safer.

[0058] The conductive member 3 may be formed in a film shape and disposed between the positive electrode B1 of the battery B and the resin member 2B. In this case, the user needs to be careful not to drop the conductive member 3 when placing the battery B in the sample chamber R. On the other hand, the cost and effort of vapor-depositing the conductive member 3 on the resin member 2B during manufacturing can be saved. The manufacturer may appropriately select whether to vapor-deposit the conductive member 3 on the resin member 2B or to form the conductive member 3 in a film shape and place it between the resin member 2B, taking into account the advantages and disadvantages of each.

[0059] The conductive member 3 preferably has a thickness of 0.1 μm or more and 10 μm or less. With this configuration, the conductive member 3 has sufficiently high X-ray transparency. Therefore, the excitation rays irradiated from the excitation source 120 and the characteristic X-rays generated from the positive electrode B1 also pass through the conductive member 3.

[0060] With this configuration, the excitation rays emitted from the excitation source 120 pass through the resin members 2A and 2B, the beryllium plate 1, and the conductive member 3, and are irradiated onto the positive electrode B1 of the battery B. Furthermore, the characteristic X-rays generated from the positive electrode B1 pass through the conductive member 3, the resin members 2A and 2B, and the beryllium plate 1, and are detected by the spectroscope. Therefore, X-ray spectroscopic analysis of the battery materials can be performed without dismantling the battery B.

[0061] [5. Comparison with conventional battery holders] The structure and composition of the battery materials in lithium-ion batteries change as they are charged and discharged, and as they deteriorate. These changes in state can be analyzed by X-ray spectroscopy. Therefore, X-ray spectroscopy of battery materials is useful in the development of lithium-ion batteries.

[0062] On the other hand, the battery material of a lithium-ion battery is highly reactive with moisture and oxygen in the air. Therefore, lithium-ion batteries for development are also configured to be laminated with metal to prevent the intrusion of air. Specifically, for example, the battery material is sealed with a stainless steel cell body and a stainless steel lid. However, since metal laminates such as stainless steel have a high absorption of X-rays, X-ray spectroscopy analysis of the battery material cannot be performed in the laminated state. Therefore, in the past, as shown in Patent Document 1, it was common to disassemble the battery and extract only the positive electrode material, which is one of the battery materials, for analysis.

[0063] However, it is technically very difficult to completely restore the state of a lithium-ion battery before disassembly using the battery materials of the battery that has been disassembled and subjected to X-ray spectroscopy analysis in this way. Specifically, for example, there is a risk that the battery materials may be damaged during restoration. In addition, for example, the contact conditions of the battery materials may change, causing changes in electrical properties such as contact resistance. Therefore, it is difficult to analyze the continuous structural changes of the battery materials during charging and discharging with this method.

[0064] Therefore, users have longed for a method that would allow them to perform X-ray spectroscopic analysis of battery materials without having to dismantle the battery.

[0065] Therefore, in the analysis device 100 according to this embodiment, a plate portion 12 including a beryllium plate 1 having resin members 2A and 2B on its surface is placed in the window W of the holder H. This makes it possible to perform non-destructive X-ray spectroscopic analysis of the battery material by irradiating the battery material with X-rays through the plate portion 12.

[0066] In addition, in this embodiment, X-ray spectroscopic analysis of the battery material can be performed while the battery B is installed in the holder H. That is, it is easy to repeatedly perform X-ray spectroscopic analysis and charging / discharging of the battery B in sequence. Therefore, discrete changes in the battery material during charging / discharging can be analyzed. In addition, as shown in FIG. 3, when the device main body 10 includes a charging / discharging device 170, it is also possible to perform X-ray spectroscopic analysis in real time while charging / discharging the battery B. In this case, continuous changes in the battery material during charging / discharging can be analyzed. Therefore, by using the holder H according to this embodiment, continuous changes in the installed battery B can be analyzed.

[0067] [6. Processing flow in the analytical device] Using the holder H in which the above-described battery B is placed, the analysis device 100 performs an X-ray spectroscopic analysis of the battery B based on the following process.

[0068] 7 is a flowchart illustrating a process related to the X-ray spectroscopic analysis. The process in FIG.

[0069] 7, first, the user opens the lid of the holder H and inserts the battery B. Next, the user charges or discharges the battery B using the charge / discharge device 170, for example.

[0070] When the charging / discharging device 170 is included in the device main body 10, the user first places the holder H in the device main body 10, connects the charging / discharging device 170, and charges / discharges the battery B. On the other hand, when the charging / discharging device 170 is provided outside the device main body 10, the user first connects the holder H to the charging / discharging device 170 to charge / discharge the battery B, and then moves the holder H into the device main body 10.

[0071] 7, in step ST02, the processor 30 of the signal processing device 20 determines whether or not the user has input an instruction to start analysis through the operation unit 26. If the instruction to start analysis has not been input (NO in step ST02), the processor 30 repeats step ST02.

[0072] If an instruction to start analysis is input (YES in step ST02), in step ST04, the processor 30 instructs the excitation source 120 of the device body 10 to irradiate excitation rays to the holder H, inside which is formed a sample chamber R in which the battery B is placed.

[0073] In step ST06, the spectroscope detects the intensity of each wavelength by dispersing the characteristic X-rays generated by the cell B. A signal indicating the intensity of each wavelength of the detected characteristic X-rays is transmitted to the signal processing device 20.

[0074] In step ST08, the processor 30 of the signal processing device 20 processes the signal indicating the intensity of each wavelength of the characteristic X-ray. In step ST10, the processor 30 stores the processing result in the memory 32. The processor 30 also displays the processing result on the display 24, and ends the processing.

[0075] Through the above process, the analysis device 100 can perform X-ray spectroscopic analysis without disassembling the battery B placed in the holder H. Furthermore, the analysis device 100 can notify the user of the results of the X-ray spectroscopic analysis.

[0076] [7. Modifications] In the following modified example, a configuration of a holder for improving the intensity of characteristic X-rays detected by a spectrometer will be described.

[0077] (Variation 1) Fig. 8 is a cross-sectional view illustrating a first modified example of the embodiment. Referring to Fig. 8, an opening 31 is formed in a conductive member 3B at a position overlapping with a window W. The shape of the opening 31 is, for example, circular or rectangular, but is not limited thereto.

[0078] The conductive member 3 shown in Fig. 6 has high X-ray transparency, but does not transmit all X-rays. Therefore, if the conductive member 3B is configured as shown in Fig. 8, the excitation rays from the excitation source 120 pass through the opening 31 of the conductive member 3B and are irradiated onto the battery B, which is the sample. In other words, the excitation rays irradiated onto the battery B are not attenuated by the conductive member 3B. Therefore, the intensity of the excitation rays is stronger than when the opening 31 is not formed in the conductive member 3.

[0079] Furthermore, characteristic X-rays generated in the battery B also pass through the opening 31 of the conductive member 3B and reach the spectroscope. That is, the characteristic X-rays that reach the spectroscope are not attenuated by the conductive member 3B. Therefore, the intensity of the characteristic X-rays is stronger than when the opening 31 is not formed in the conductive member 3.

[0080] That is, by forming the opening 31 in the conductive member 3B, even when excitation rays of the same intensity are irradiated from the excitation source 120, characteristic X-rays of stronger intensity can be detected than when the opening 31 is not formed in the conductive member 3. Therefore, analysis results with a higher S / N ratio can be obtained.

[0081] When the holder H is configured in this manner, there is no need to consider the attenuation of the excitation rays and characteristic X-rays by the conductive member 3B, so the thickness of the conductive member 3B may be greater than when the opening 31 is not formed. For example, the thickness of the conductive member 3B may be 10 μm or more. By configuring the conductive member 3B to be thick, the rigidity of the conductive member 3B also increases. In other words, the user and manufacturer can easily handle the conductive member 3B. In addition, defects in the conductive member 3B, such as the end of the conductive member 3B being inappropriately turned over, are less likely to occur when assembling the holder H.

[0082] In addition, since there is no need to consider the attenuation of excitation rays and characteristic X-rays by the conductive member 3B, a material with lower X-ray transmittance and higher conductivity than aluminum, such as copper, can be used for the conductive member 3B. This configuration expands the options for materials that can be used for the conductive member 3B.

[0083] (Variation 2) 9 is a cross-sectional view illustrating a second modified example of the embodiment. Referring to FIG. 9, a resin member 2C is disposed inside an opening 31 of a conductive member 3B. The resin member 2C corresponds to one example of a "second resin member." It is preferable that the resin member 2C has the same thickness as the opening 31.

[0084] As an example, the resin member 2C is formed in a film shape and disposed between the positive electrode B1 and the resin member 2B. In this case, the resin member 2C has a size, for example, larger than the irradiation range of the X-rays and smaller than the opening 31. Another example of the resin member 2C is one formed by filling the opening 31 with a paste-like resin. In this case, the resin member 2C has, for example, the same size as the opening 31.

[0085] With this configuration, the part of battery B corresponding to opening 31 can be prevented from being deformed, such as distorted, by the pressing force of spring 55 from below (negative side of the Z axis) against battery B, by physical interference from the intervening object (resin member 2C).

[0086] The resin member 2C is preferably made of a resin that has high X-ray transparency and is less damaged by X-rays. The resin member 2C is made of, for example, a polyimide resin. With this configuration, the excitation rays from the excitation source 120 pass through the plate portion 12 and the resin member 2C and are irradiated onto the battery B, which is the sample. In addition, the characteristic X-rays generated in the battery B also pass through the resin member 2C and the plate portion 12 and reach the spectroscope. In other words, X-ray spectroscopic analysis of the battery material is possible without dismantling the battery B.

[0087] [Aspects] It will be appreciated by those skilled in the art that the exemplary embodiments described above are examples of the following aspects.

[0088] (Item 1) A holder according to one embodiment is a holder for holding a battery to be analyzed by X-ray analysis. The battery includes a positive electrode and a negative electrode. The holder has a sample chamber formed therein for placing the battery. The holder includes a body, a beryllium plate, a first resin member, a conductive member, a positive electrode terminal, and a negative electrode terminal. The body has a window formed on an upper surface. The beryllium plate is placed in the window. The first resin member is provided on a surface of the beryllium plate. The conductive member is provided between the positive electrode and the first resin member so as to contact the positive electrode of the battery. The positive electrode terminal is electrically connected to the conductive member. The negative electrode terminal is electrically connected to the negative electrode.

[0089] According to the holder described in paragraph 1, X-ray spectrometry of the battery can be performed by irradiating the battery material with X-rays through the beryllium plate placed in the window of the holder. Therefore, the battery material can be analyzed without dismantling the battery.

[0090] (Item 2) In the holder described in item 1, the first resin member may be configured to include a polyimide resin.

[0091] Polyimide resin has high X-ray transparency. That is, according to the holder described in paragraph 2, it is easy to perform X-ray spectroscopic analysis of the battery through the plate portion consisting of the first resin member and the beryllium plate. In addition, polyimide resin is a sturdy resin having excellent mechanical strength and excellent chemical resistance. Therefore, by providing a resin member containing polyimide resin on the surface, it is possible to reduce the possibility of the beryllium plate being exposed. That is, according to the holder described in paragraph 2, the plate portion is also easy to handle.

[0092] (Item 3) In the holder described in item 1 or 2, the first resin member may be made of a material containing a fluororesin.

[0093] Depending on the type of resin, the intensity of the irradiated excitation rays, the temperature, etc., the moisture contained in the first resin member may cause side reactions other than the battery reaction, which may adversely affect the measurement accuracy. Therefore, according to the holder described in paragraph 3, this problem can be suppressed by using a highly water-repellent fluororesin as the first resin member.

[0094] (Item 4) In the holder according to any one of items 1 to 3, the total thickness of the first resin member in a direction perpendicular to the beryllium plate may be 100 μm or less.

[0095] According to the holder described in paragraph 4, the X-ray transmittance of the first resin member is sufficiently high. (Item 5) In the holder according to any one of items 1 to 4, the conductive member may be made of aluminum.

[0096] Aluminum is the second most X-ray-transmitting metal after beryllium. On the other hand, aluminum is easier to handle than beryllium because there is less concern about its effect on the human body. According to the holder described in paragraph 5, X-ray spectrometry can be performed on the battery while it is still placed in the holder. In addition, the conductive member is easy to handle.

[0097] (Item 6) In the holder according to any one of items 1 to 5, the conductive member may be 0.1 μm or more and 10 μm or less.

[0098] According to the holder described in the sixth aspect, the X-ray transmittance of the conductive member is sufficiently high. (Item 7) In the holder according to any one of items 1 to 6, the conductive member may be deposited on the first resin member.

[0099] According to the holder described in paragraph 7, the holder is easier for the user to handle than when the conductive member is separate from the first resin member.

[0100] (Item 8) In the holder according to any one of items 1 to 7, the conductive member may be formed in a film shape and disposed between the positive electrode and the first resin member.

[0101] According to the holder described in item 8, the cost and effort of vapor-depositing a conductive member onto the first resin member during manufacturing can be eliminated.

[0102] (Item 9) In the holder according to any one of items 1 to 8, the conductive member may have an opening formed at a position overlapping with the window.

[0103] According to the holder described in paragraph 9, even when excitation rays of the same intensity are irradiated from the irradiation source, characteristic X-rays of stronger intensity can be detected at the opening than when no opening is formed in the conductive member, thereby making it possible to obtain analysis results with a higher S / N ratio.

[0104] (Item 10) In the holder described in item 9, the holder may further include a second resin member, and the second resin member may be disposed inside the opening.

[0105] According to the holder described in paragraph 10, the battery in the portion corresponding to the opening can be prevented from being deformed, such as distorted, by the pressing force of the spring from below against the battery, by physical interference from the second resin member which serves as an intermediary.

[0106] (Item 11) An analysis device according to one embodiment includes a holder, a spectroscope, and a signal processing device. The holder holds a battery. The spectroscope irradiates the battery held in the holder with excitation rays, and separates the generated characteristic X-rays to detect the intensity for each wavelength. The signal processing device processes the signal output from the spectroscope. The battery includes a positive electrode and a negative electrode. The holder includes a body, a beryllium plate, a resin member, a conductive member, a positive electrode terminal, and a negative electrode terminal. The body has a sample chamber formed therein for disposing the battery, and a window formed in the direction of incidence of the excitation rays. The beryllium plate is disposed in the window. The resin member is provided on the surface of the beryllium plate. The conductive member is provided between the positive electrode and the resin member so as to be in contact with the positive electrode. The positive electrode terminal is electrically connected to the conductive member. The negative electrode terminal is electrically connected to the negative electrode.

[0107] According to the analytical device described in paragraph 11, X-ray spectroscopic analysis of a battery can be performed by irradiating the battery material with X-rays through a beryllium plate placed in the window of the holder. Therefore, the battery material can be analyzed without dismantling the battery.

[0108] (Item 12) An analysis method according to one embodiment is a method for analyzing a battery, and includes the steps of irradiating an excitation ray to a battery held in a holder, detecting the intensity of each wavelength by dispersing characteristic X-rays generated from the battery, and processing a signal indicating the intensity of the characteristic X-rays at each wavelength. The battery includes a positive electrode and a negative electrode. The holder includes a body, a beryllium plate, a resin member, a conductive member, a positive electrode terminal, and a negative electrode terminal. The body has a sample chamber formed therein for placing the battery, and a window formed in the direction of incidence of the excitation ray. The beryllium plate is placed in the window. The resin member is provided on the surface of the beryllium plate. The conductive member is provided between the positive electrode and the resin member so as to be in contact with the positive electrode. The positive electrode terminal is electrically connected to the conductive member. The negative electrode terminal is electrically connected to the negative electrode.

[0109] According to the analysis method described in paragraph 12, X-ray spectrometry of a battery can be performed by irradiating the battery material with X-rays through a beryllium plate placed in the window of the holder. Therefore, the battery material can be analyzed without dismantling the battery.

[0110] The embodiments disclosed herein should be considered to be illustrative and not restrictive in all respects. The scope of the present invention is defined by the claims, not the above description, and is intended to include all modifications within the meaning and scope of the claims. [Explanation of symbols]

[0111] 1 beryllium plate, 12 plate portion, 2A, 2B, 2C resin member, 3, 3B conductive member, 4 body, 10 device main body, 20 signal processing device, 22 controller, 24 display, 26 operation unit, 30 processor, 31 opening, 32 memory, 34 communication I / F, 36 input / output I / F, 41 window body, 42 cell body, 50 insulating plate, 51 base plate, 52 insulating spacer, 53 inner cylinder, 54 electrode guide, 55 spring, 56 electrode support portion, 100 analyzer, 120 excitation source, 130 slit, 140 analyzing crystal, 150 detector, 151 detection element, 170 charge / discharge device, B battery, B1 positive electrode, B2 negative electrode, B3 separator, B11 positive electrode material, B12 positive electrode current collector, B21 Negative electrode material, B22 negative electrode current collector, H holder, R sample chamber, T1 positive electrode terminal, T2 negative electrode terminal, W window.

Claims

1. A holder for holding a battery to be analyzed by X-ray analysis, The battery includes a positive electrode and a negative electrode, The holder includes: a body having a sample chamber formed therein for placing the battery therein and a window formed on an upper surface thereof; a beryllium plate disposed in the window; a first resin member provided on a surface of the beryllium plate; a conductive member provided between the positive electrode and the first resin member so as to be in contact with the positive electrode of the battery; A positive electrode terminal electrically connected to the conductive member; a negative electrode terminal electrically connected to the negative electrode.

2. The holder according to claim 1 , wherein the first resin member is made of a material containing a polyimide resin.

3. The holder according to claim 1 , wherein the first resin member contains a fluororesin.

4. 2. The holder according to claim 1, wherein the total thickness of said first resin member in a direction perpendicular to said beryllium plate is 100 [mu]m or less.

5. The holder according to claim 1 , wherein the conductive member comprises aluminum.

6. The holder according to claim 1 , wherein the conductive member has a thickness of 0.1 μm or more and 10 μm or less.

7. The holder according to claim 1 , wherein the conductive member is vapor-deposited on the first resin member.

8. The holder according to claim 1 , wherein the conductive member is formed in a film shape and is disposed between the positive electrode and the first resin member.

9. The holder according to claim 1 , wherein the conductive member has an opening formed at a position overlapping with the window.

10. The holder further includes a second resin member, The holder according to claim 9 , wherein the second resin member is disposed inside the opening.

11. A battery analysis device, comprising: a holder for holding the battery; a spectroscope that irradiates the battery held by the holder with an excitation ray and disperses the generated characteristic X-rays to detect the intensity of each wavelength; a signal processing device that processes a signal output from the spectrometer; The battery includes a positive electrode and a negative electrode, The holder includes: a body having a sample chamber formed therein for disposing the battery therein and a window formed in a direction in which the excitation beam is incident; a beryllium plate disposed in the window; a resin member provided on a surface of the beryllium plate; a conductive member provided between the positive electrode and the resin member so as to be in contact with the positive electrode; A positive electrode terminal electrically connected to the conductive member; and a negative electrode terminal electrically connected to the negative electrode.

12. A method for analyzing a battery, comprising: irradiating the battery held in a holder with an excitation beam; A step of detecting an intensity of each wavelength by dispersing characteristic X-rays generated from the battery; and processing a signal indicating the intensity of each wavelength of the characteristic X-ray; The battery includes a positive electrode and a negative electrode, The holder includes: a body having a sample chamber formed therein for disposing the battery therein and a window formed in a direction in which the excitation beam is incident; a beryllium plate disposed in the window; a resin member provided on a surface of the beryllium plate; a conductive member provided between the positive electrode and the resin member so as to be in contact with the positive electrode; A positive electrode terminal electrically connected to the conductive member; and a negative electrode terminal electrically connected to the negative electrode.

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