JP6319147B2 - X-ray analysis system and program - Google Patents

Description

  The present invention relates to an X-ray analysis system and program used for X-ray analysis of a sample, and in particular, X-ray analysis suitable for use in measuring the electronic state or structural change of a secondary battery in a charge / discharge process System and program.

  Among secondary batteries, a lithium ion secondary battery is known as a battery having a high energy density and a high operating voltage. Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and notebook personal computers, as well as power sources for hybrid vehicles and electric vehicles.

  Generally, a lithium ion secondary battery is composed of a positive electrode having a positive electrode active material as a main component, a negative electrode having a negative electrode active material as a main component, a separator separating the positive electrode and the negative electrode, a non-aqueous electrolyte, and the like. Yes. These constituent materials are sealed with an exterior material such as a metal can or an aluminum laminate film. Those using metal cans as exterior materials are called hard pack types, and those using aluminum laminate films are also called soft pack types or laminate cells.

  In the development of battery materials, X-ray analysis is employed to evaluate battery materials. Among X-ray analysis, in particular, X-ray diffraction (X-ray Diffraction: hereinafter referred to as XRD) measurement and X-ray absorption fine structure (hereinafter abbreviated as XAFS) measurement include crystal structure, It is an analytical technique that gives information such as the valence and local structure (coordination number, interatomic distance) of each constituent element, and is widely used for the evaluation of battery materials.

  The method of X-ray analysis of battery materials is roughly divided into ex-situ measurement and in-situ measurement. In ex-situ measurement, charged and discharged battery cells are disassembled, and constituent materials such as positive electrodes are taken out and subjected to X-ray analysis. In-situ measurement is to perform X-ray analysis while charging and discharging without disassembling the battery. In the case of a secondary battery using a non-aqueous electrolyte such as a lithium ion secondary battery, in the ex-situ measurement, if a constituent material such as a positive electrode is taken out from the battery outer packaging material and exposed to the atmosphere, the positive electrode activity in the positive electrode The state of the substance may change. For this reason, in-situ measurement capable of evaluating a state close to an actual battery reaction is becoming mainstream in recent years.

  Regarding in-situ X-ray analysis, as described in Non-Patent Document 1, for example, a special electrochemical cell for X-ray analysis using metal beryllium has been developed and used for evaluation of battery materials. ing. Metal beryllium is conductive and has a high X-ray transmittance, so it is used as a material for a window portion that transmits X-rays. However, when metal beryllium is used as the material for the window, (1) it is difficult to handle because the oxide of beryllium is a poison, and (2) the cell fabrication cost is high due to the complicated structure of the electrochemical cell. There was a problem such as.

  On the other hand, as described in Patent Document 1, a method of directly performing X-ray analysis for a thin plate battery (laminate cell) covered with an aluminum laminate film or the like is also employed. The laminate cell has a sufficiently high transmittance when irradiated with X-rays because the positive electrode, the negative electrode, the exterior, and the like are sufficiently thin. Therefore, X-ray analysis can be performed as it is without decomposing the laminate. This method has an advantage that a plurality of cells can be easily manufactured because the handling of the laminate cell is simple and the manufacturing cost of the cell is low.

JP-A-11-230919

M. N. Richard et al, J. Electrochem. Soc. 144, 554, (1997)

However, conventionally, there are the following problems when performing X-ray analysis of a laminate cell in-situ.
In XAFS measurement, which is one of the X-ray analyses, X-ray absorbance of a laminate cell being charged / discharged is measured while charging / discharging the laminate cell. In the XAFS measurement, in order to investigate the change of the battery material over time due to charge / discharge, the laminate cell is charged / discharged over a predetermined charge / discharge test time (for example, around 20 hours). The linear absorbance is measured. For this reason, in order to obtain the measurement result of the X-ray analysis for a plurality of laminate cells, at least the time required for multiplying the number of laminate cells by the charge / discharge test time is required. Therefore, it takes a long time to obtain measurement results for all the laminate cells.

  In the X-ray analysis of the laminate cell, X-rays with very high energy are used. Specifically, X-rays obtained from synchrotron radiation from the Synchrotron Radiation Research Facility of the High Energy Accelerator Research Organization are used. There are only a few such large synchrotron facilities in Japan. For this reason, when a manufacturer, institution, or organization that conducts research and development (hereinafter collectively referred to as “manufacturers, etc.”) uses a large-scale synchrotron radiation facility, a manufacturer or the like uses the measurement location in the large-scale synchrotron radiation facility. During this period, other manufacturers cannot use it. Therefore, it is important to efficiently perform the X-ray analysis of the laminate cell in order to effectively use the few large synchrotron radiation facilities.

  A main object of the present invention is to provide a technique capable of performing X-ray analysis of a plurality of laminate cells more efficiently than before.

The first aspect of the present invention is:
An in-situ X-ray that obtains analytical data by irradiating the laminated cell with X-rays using a laminated cell in which a battery element formed by laminating a positive electrode and a negative electrode with a separator interposed therebetween is sealed with a laminate film together with an electrolytic solution. An X-ray analysis system used for analysis,
A sample having a sample holder capable of holding a plurality of laminate cells, and of the plurality of laminate cells held by the sample holder, the laminate cell arranged at the X-ray passing position is switched by moving the sample holder. A switching device;
A charge / discharge device for charging / discharging the plurality of laminate cells held by the sample holder within a predetermined charge / discharge test time;
A control device for controlling the sample switching device and the charge / discharge device so as to perform X-ray analysis measurements of the plurality of laminate cells in parallel within the charge / discharge test time;
The system for X-ray analysis characterized by comprising.

The second aspect of the present invention is:
The control device drives the sample switching device to switch the laminate cell to be arranged at the X-ray passing position each time measurement of one X-ray analysis is completed for one laminate cell, and The sample switching device is controlled so that the sample switching device repeats at least two times or more within the charge / discharge test time in order to sequentially arrange the laminate cells at the X-ray passage positions. The X-ray analysis system according to the first aspect.

The third aspect of the present invention is:
The said control apparatus controls the said charging / discharging apparatus so that the charging / discharging of these laminate cells may be started in order according to the order of the laminate cells arrange | positioned in the passage position of the said X-ray. The X-ray analysis system according to the first or second aspect.

The fourth aspect of the present invention is:
The control device controls the operation of the sample switching device so as to be interlocked with the operation of a monochromator that adjusts the energy of X-rays applied to the laminate cell. The X-ray analysis system according to any one of the above.

According to a fifth aspect of the present invention,
An in-situ X-ray that obtains analytical data by irradiating the laminated cell with X-rays using a laminated cell in which a battery element formed by laminating a positive electrode and a negative electrode with a separator interposed therebetween is sealed with a laminate film together with an electrolytic solution. A program used for an X-ray analysis system used for analysis,
A sample having a sample holder capable of holding a plurality of laminate cells, and of the plurality of laminate cells held by the sample holder, the laminate cell arranged at the X-ray passing position is switched by moving the sample holder. A switching device;
A charge / discharge device that charges and discharges the plurality of laminate cells held by the sample holder within a predetermined charge / discharge test time, and is subject to control,
A program for causing a computer to function as a control device for controlling the sample switching device and the charge / discharge device so as to perform X-ray analysis measurements of the plurality of laminate cells in parallel within the charge / discharge test time. is there.

  According to the present invention, X-ray analysis of a plurality of laminate cells can be performed more efficiently than before.

It is the schematic which shows the structural example of an X-ray analyzer. It is a schematic sectional drawing which shows the structural example of the lamination cell used as the object sample of X-ray analysis. It is a figure which shows the structural example of the system for X-ray analysis which concerns on embodiment of this invention. It is a front view which shows the structural example of the sample switching apparatus which concerns on embodiment of this invention. It is a perspective view of the sample switching device shown in FIG. It is a front view of a 1st support member. It is a perspective view of a 1st support member. It is a perspective view of the 2nd support member. It is a front view which shows the state which affixed the window member on the 1st support member. It is a front view which shows the state which affixed the window member on the 2nd support member. It is sectional drawing of a holding | suppressing part. It is a schematic diagram which shows the state which connected the some laminate cell electrically to the charging / discharging apparatus. It is a flowchart which shows the procedure of the process performed at a measurement process. It is FIG. (1) explaining the switching operation | movement of the lamination cell accompanying the movement of a sample holder. It is FIG. (2) explaining switching operation | movement of the lamination cell accompanying the movement of a sample holder. It is FIG. (3) explaining switching operation | movement of the lamination cell accompanying the movement of a sample holder. It is FIG. (4) explaining switching operation | movement of the lamination cell accompanying the movement of a sample holder. It is a timing chart in the case of starting charging / discharging of four laminate cells simultaneously. It is a timing chart in the case of starting charging / discharging of four laminate cells in order at a different timing. It is a perspective view which shows the structural example of the sample switching apparatus which concerns on other embodiment of this invention. It is a perspective view of a 1st support member. It is a front view of a sample holder. (A) is a top view of a 1st support member, (B) is a front view of a 1st support member.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
In the embodiment of the present invention, description will be given in the following order.
1. 1. Configuration of X-ray analyzer 2. Laminate cell configuration 3. Configuration of X-ray analysis system 4. Configuration of sample switching device 5. Operation of sample switching device 6. X-ray analysis method Effects of the embodiment 8. 8. Modifications etc. Other embodiments

<1. Configuration of X-ray analyzer>
FIG. 1 is a schematic diagram showing a configuration example of an X-ray analyzer.
The illustrated X-ray analyzer includes an X-ray emission light source 1, a monochromator 2, a first X-ray detector 3, a sample placement unit 4, and a second X-ray detector 5. . The X-ray radiation light source 1 emits high-energy X-rays. In X-ray analysis, X-rays generated from a laboratory X-ray apparatus or a synchrotron radiation facility can be used. The monochromator 2 adjusts the energy (wavelength) of X-rays applied to the sample by diffraction based on Bragg's conditional expression. Specifically, the monochromator 2 takes out X-rays emitted from the X-ray radiation light source 1 and diffracts the taken-in X-rays to take out X-rays having a specific energy (wavelength). As the monochromator 2, a double crystal monochromator can be used. When a double crystal monochromator is used, X-rays having a specific energy (wavelength) can be extracted according to the angle of the two spectral crystals, and the position of the outgoing beam can be kept constant. Also, by controlling the operation of the monochromator 2 according to the Bragg conditional expression, the angle of the monochromator 2 can be changed continuously or intermittently.

  A first X-ray detector 3, a sample placement unit 4, and a second X-ray detector 5 are sequentially arranged in the X-ray emission direction whose energy is adjusted by the monochromator 2. The sample placement unit 4 is a part for placing a sample to be subjected to X-ray analysis. In the present embodiment, a laminate cell 10 is used as a target sample for X-ray analysis. The first X-ray detector 3 detects the intensity of X-rays incident on the laminate cell 10. The second X-ray detector 5 detects the intensity of X-rays that have passed through the laminate cell 10.

  In the X-ray analysis apparatus having the above-described configuration, after the laminate cell 10 is installed in the sample installation unit 4, X-rays are emitted from the X-ray radiation light source 1. X-rays radiated from the X-ray radiation light source 1 enter the laminate cell 10 with the energy adjusted by the monochromator 2. At this time, the intensity of the X-rays incident on the laminate cell 10 is detected by the first X-ray detector 3. Further, the intensity of the X-ray transmitted through the laminate cell 10 is detected by the second X-ray detector 5. Thus, the X-ray absorbance of the laminate cell 10 can be obtained from the ratio between the incident X-ray intensity detected by the first X-ray detector 3 and the transmitted X-ray intensity detected by the second X-ray detector 5. it can.

<2. Laminate cell configuration>
FIG. 2 is a schematic cross-sectional view showing a configuration example of a laminate cell that is a target sample for X-ray analysis. The illustrated laminate cell 10 includes a battery element 14 including a positive electrode 11, a negative electrode 12, and a separator 13. The positive electrode 11 is formed, for example, in the form of a sheet having a rectangular shape when viewed from the front using, for example, an aluminum foil. A positive electrode active material layer 15 is formed on one surface of the positive electrode 11. The positive electrode active material layer 15 constitutes a part of the positive electrode 11 and is formed of a coating film using, for example, lithium nickelate, a conductive auxiliary agent, and a binder. The negative electrode 12 is formed in a generally rectangular sheet shape as viewed from the front, for example, using copper foil. A negative electrode active material layer 16 is formed on one surface of the negative electrode 12. The negative electrode active material layer 16 constitutes a part of the negative electrode 12 and is formed of, for example, a coating film using graphite and a binder. The separator 13 is formed in a rectangular sheet shape when viewed from the front. The battery element 14 has a structure in which the positive electrode 11 and the negative electrode 12 are stacked with the separator 13 interposed therebetween. In this laminated structure, the positive electrode active material layer 15 of the positive electrode 11 and the negative electrode active material layer 16 of the negative electrode 12 are disposed so as to face each other with the separator 13 therebetween.

  Further, the battery element 14 is sealed with a laminate film 18 together with the electrolytic solution 17. However, the terminal portion Ta of the positive electrode 11 and the terminal portion Tb of the negative electrode 12 are each drawn out of the laminate film 18 in order to connect a terminal (not shown) for charging and discharging. The laminate film 18 is formed in a bag shape that is slightly larger than the battery element 14 and has a rectangular shape in front view. An appropriate amount of electrolytic solution 17 made of a non-aqueous electrolytic solution is injected into the laminate film 18. Thus, the laminate cell 10 constitutes a laminate sheet type lithium ion secondary battery. The laminate cell 10 has a thin plate-like structure in which the positive electrode 11, the negative electrode 12, and the separator 13 are each composed of a single sheet so as to transmit X-rays to the extent required for X-ray analysis. .

<3. Configuration of X-ray analysis system>
FIG. 3 is a diagram showing a configuration example of the entire X-ray analysis system including the X-ray analysis system according to the embodiment of the present invention.
The illustrated X-ray analysis system is a system that performs X-ray analysis of the laminate cell 10 using the above-described X-ray analysis apparatus. This X-ray analysis system includes an X-ray analysis system 20, a measuring instrument 22, an X-ray control unit 23, a data acquisition unit 24, in addition to the components (1 to 5) of the X-ray analysis apparatus described above. It is the structure provided with. The X-ray analysis system 20 includes a control device 25, a charge / discharge device 26, and a sample switching device 27.

  The measuring instrument 22 takes in the intensity data of the incident X-ray detected by the first X-ray detector 3 and the intensity data of the transmitted X-ray detected by the second X-ray detector 5 as described above. Measurement data indicating the X-ray absorbance of the laminate cell 10 is generated. The X-ray control unit 23 controls the operation (angle) of the monochromator 2 in accordance with a predetermined X-ray control condition, so that the X-ray energy irradiated to the sample (laminate cell 10) is within a predetermined range. Variable control is performed. The data acquisition unit 24 acquires the X-ray absorbance measurement data generated by the measuring instrument 22 and the angle data of the monochromator 2 controlled based on the control conditions of the X-ray control unit 23, and acquires them. Data is stored in association with each other. For example, the X-ray control unit 23 continuously (or intermittently) changes the angle of the monochromator 2 to θa, θb, θc,..., And the measuring instrument 22 changes the X-ray absorbance measurement data to Da corresponding to this. , Db, Dc,... In such a case, the data acquisition unit 24 uses the angle data θa and X-ray absorbance measurement data Da of the monochromator 2, the angle data θb and X-ray absorbance measurement data Db of the monochromator 2, and the angle data θc and X of the monochromator 2. The linear absorbance measurement data Dc is stored in association with each other. Thus, the data acquired and stored by the data acquisition unit 24 is analysis data relating to the X-ray absorbance of the laminate cell 10. Incidentally, the energy (wavelength) of X-rays adjusted by the monochromator 2 depends on the angle of the monochromator 2. Therefore, the angle data of the monochromator 2 can be converted into data indicating the energy or wavelength of X-rays irradiated on the sample.

(Control device)
The control device 25 comprehensively controls the processing operation of the entire X-ray analysis system 20. The control device 25 controls the charge / discharge device 26 and the sample switching device 27, respectively. And the control apparatus 25 controls the charging / discharging apparatus 26 and the sample switching apparatus 27 so that the measurement of the several lamination cell 10 may be performed in parallel within the predetermined charging / discharging test time. Further, the control device 25 controls the operation of the sample switching device 27 so as to be interlocked with the operation of the monochromator 2. A specific control method will be described in detail later.

  The control device 25 mainly includes a charge / discharge control unit 28 and a sample switching control unit 29. The charge / discharge control unit 28 controls the charge / discharge device 26 according to predetermined charge / discharge conditions. The sample switching control unit 29 controls the operation of the sample switching device 27 in accordance with a predetermined switching condition.

  The functions of the control device 25 and the control units 28 and 29 are a program stored in a ROM (Read Only Memory) or a hard disk, which is a hardware resource of a computer, and a CPU (Central Processing Unit) that is a RAM (Random Access Memory). This can be realized by reading and executing the above. In addition, the program for that purpose may be installed in a computer in advance, may be provided by being stored in a computer-readable recording medium, or may be provided via a wired or wireless communication network. .

  The charge / discharge device 26 performs charge / discharge of the laminate cell 10. The charging / discharging of the laminate cell 10 is performed in order within a predetermined charging / discharging test time. Further, this charging / discharging is performed as one pattern of “charge” → “stop” → “discharge”. Specifically, the laminate cell 10 is “charged” at a constant current, and when a predetermined cutoff condition (cutoff voltage or the like) is satisfied, the charging is “stopped” and the predetermined cutoff condition is set. "Discharge" until. The charging / discharging device 26 is configured by a multi-channel charging / discharging device capable of electrically connecting a plurality of laminate cells 10 at the same time. By using a multi-channel type charging / discharging device, charging / discharging of a plurality of laminate cells 10 can be performed in parallel.

  The sample switching device 27 switches the laminate cell 10 disposed at the X-ray passing position from the first X-ray detector 3 toward the second X-ray detector 5. Hereinafter, a specific configuration of the sample switching device 27 will be described.

<4. Configuration of sample switching device>
FIG. 4 is a front view showing a configuration example of the sample switching device according to the embodiment of the present invention, and FIG. 5 is a perspective view of the sample switching device shown in FIG. The sample switching device 27 generally includes a sample holder 31 and a holder moving device 32 that supports the sample holder 31 so as to be movable.

(Holder moving device)
The holder moving device 32 is mounted on the pedestal 33. The pedestal 33 is provided in the sample setting unit 4 of the X-ray analyzer. The holder moving device 32 includes a motor (not shown), a rotating plate 34 that rotates using the motor as a drive source, and a stage mechanism 39 that supports the rotating plate 34. For example, a stepping motor, a servo motor, or the like can be used as a motor serving as a drive source. The rotating plate 34 is formed in a disc shape, and the center thereof is a rotation center 35. A plurality (four in the illustrated example) of screw holes 36 are provided on the front surface of the rotating plate 34. These screw holes 36 are for attaching the sample holder 31 to the rotating plate 34.

  The stage mechanism 39 of the holder moving device 32 corresponds to a position adjusting mechanism that can adjust the position of the rotating plate 34 in a direction orthogonal to the optical axis direction of the X-ray incident (irradiated) on the laminate cell 10. The stage mechanism 39 is configured using an XY stage. The stage mechanism 39 is configured using an XY stage. The stage mechanism 39 has a vertical direction (vertical direction) and a horizontal direction (horizontal direction) in a plane perpendicular to the optical axis direction of the X-ray when the holder moving device 32 is installed in the sample setting unit 4 of the X-ray analyzer. The rotating plate 34 is movably supported. Of the XY stages constituting the stage mechanism 39, one stage moves the rotating plate 34 in the vertical direction according to the rotation of the micrometer head 37, and the other stage rotates the rotating plate 34 according to the rotation of the micrometer head 38. Is moved horizontally. Therefore, the position of the rotating plate 34 can be adjusted independently in the vertical direction and the horizontal direction by appropriately rotating the micrometer heads 37 and 38.

(Sample holder)
The sample holder 31 is used to hold the laminate cell 10 when performing X-ray analysis using the above-described laminate cell 10 as a target sample. In the present embodiment, as an example of “X-ray analysis”, a case will be described in which the present invention is applied to in-situ X-ray analysis in which the laminate cell 10 is irradiated with X-rays to obtain analysis data. “In-situ X-ray analysis” refers to performing X-ray analysis without decomposing the laminate cell 10 constituting the lithium ion secondary battery.

  The sample holder 31 is configured to be able to hold a plurality of laminate cells 10. In the present embodiment, a maximum of four laminate cells 10 can be simultaneously held using one sample holder 31. Hereinafter, when the four laminate cells 10 are described separately, the reference numerals 10A, 10B, 10C, and 10D are attached to the individual laminate cells 10 as appropriate.

  The sample holder 31 includes a first support member 41, four second support members 42, and a pressing portion 43 that presses the first support member 41 and the second support member 42. . The first support member 41 is a member corresponding to the four laminate cells 10 in common. The second support member 42 is a member corresponding to each of the four laminate cells 10.

(First support member)
FIG. 6 is a front view of the first support member 41, and FIG. 7 is a perspective view of the first support member 41.
The first support member 41 is formed in a flat plate shape having an appropriate thickness (for example, a thickness of about 5 to 10 mm). The first support member 41 is formed in a fan shape when viewed from the front. Specifically, the first support member 41 is mainly formed in a fan shape by one arc 44 and two sides 45 and 46 having one ends connected to both ends of the arc 44. The central angle of the sector forming the first support member 41 is less than 180 ° (about 125 ° in this embodiment). A base portion 47 of the first support member 41 is formed at the other end of the two sides 45 and 46. A part of the base 47 is formed in a circular arc shape (semi-circular shape) whose radius of curvature is smaller than that of the circular arc 44 and whose direction is opposite to that of the circular arc 44.

  One main surface (hereinafter, also simply referred to as “main surface”) 48 of the first support member 41 is sized so that the four laminate cells 10 can be arranged in a plane. The main surface 48 of the first support member 41 is a support surface for supporting the laminate cell 10 with the second support member 42 described above. On the main surface 48 of the first support member 41, four sample attachment regions 49 are virtually partitioned. The sample attachment area 49 is an area secured for attaching the laminate cell 10. The four sample mounting areas 49 are radially spaced with an appropriate interval between the adjacent sample mounting areas 49 so that the four laminated cells 10 can be arranged radially on the main surface 48 of the first support member 41. Are lined up.

  Each sample attachment region 49 is provided with one X-ray transmission hole 51 and four screw attachment holes 52. A total of four X-ray transmission holes 51 are provided for the entire first support member 41 in accordance with the number of laminate cells 10 that can be held by one sample holder 31. Both the X-ray transmitting hole 51 and each screw mounting hole 52 are formed so as to penetrate the first support member 41 in the thickness direction. The X-ray transmission hole 51 is provided in the first support member 41 as an X-ray transmission part for transmitting X-rays. The X-ray transmission hole 51 is provided at the center of the sample attachment region 49. One screw mounting hole 52 is provided at each of the four corners of the sample mounting region 49. The screw attachment hole 52 is for attaching a screw 43 (see FIG. 11) described later.

  A rotation center 53 of the sample holder 31 is set at the center of the base 47 of the first support member 41. Four connection holes 54 are provided around the rotation center 53 of the base 47. These connection holes 54 are for connecting the sample holder 31 to the rotating plate 34 of the holder moving device 32. The four X-ray transmitting holes 51 described above are formed at a position equidistant from the rotation center 53 and at an equal angular interval θ1 (θ1 = 40 ° interval in this embodiment). ing.

(Second support member)
FIG. 8 is a perspective view of the second support member.
The second support member 42 is formed in a flat plate shape having an appropriate thickness (for example, a thickness of about 10 mm). Moreover, the 2nd support member 42 is formed in the front view rectangle. One main surface (hereinafter also simply referred to as “main surface”) 55 of the second support member 42 serves as a support surface for supporting the laminate cell 10 with the first support member 41 described above. ing.

  The second support member 42 is provided with one X-ray transmitting hole 56 and four screw mounting holes 57. Both the X-ray transmitting hole 56 and each screw mounting hole 57 are formed so as to penetrate the second support member 42 in the thickness direction. The X-ray transmission hole 56 is provided in the second support member 42 as an X-ray transmission part for transmitting X-rays. The X-ray transmission hole 56 is provided at the center of the second support member 42. Further, the X-ray transmission hole 56 is formed in a circular shape with the same size (for example, a diameter of 5 mm) as the X-ray transmission hole 51 provided in the first support member 41. One screw mounting hole 57 is provided at each of the four corners of the second support member 42. The screw mounting hole 57 is for mounting a screw 43 (see FIG. 11) described later.

  The external dimension when the second support member 42 is viewed from the front is set to be approximately the same as the external dimension of the sample attachment region 49 partitioned by the first support member 41. The screw mounting hole 57 of the second support member 42 is formed in a circle with the same size (for example, a diameter of 4 mm) as the screw mounting hole 52 of the first support member 41. The positional relationship between the X-ray transmission hole 56 and the four screw mounting holes 57 in the second support member 42 is such that the X-ray transmission hole 51 and the four screw mounting holes 52 in the first support member 41 are It is set the same as the positional relationship.

(Window member)
Of the first support member 41 and the second support member 42 having the above-described configuration, four window members 58 are attached to one main surface 48 of the first support member 41 as shown in FIG. Correspondingly, a window member 59 is attached to the main surface 55 of the second support member 42 as shown in FIG. The window member 58 is attached so as to close the opening of the X-ray transmission hole 51, and the window member 59 is attached so as to close the opening of the X-ray transmission hole 56. The window members 58 and 59 are members that directly contact the laminate cell 10 when the laminate cell 10 is supported between the first support member 41 and the second support member 42. One window member 58 is affixed to each sample attachment region 49 corresponding thereto. The window members 58 and 59 are formed in the same shape and size using the same material. More specifically, each of the window members 58 and 59 has a thin sheet shape and is formed in a rectangular shape in plan view. Each of the window members 58 and 59 is made of a material having both an X-ray transmittance that does not hinder measurement in X-ray analysis and mechanical rigidity. As a material for the window members 58 and 59, carbon fiber reinforced plastic can be suitably used.

  Here, the dimension example of the laminate cell 10, the 2nd support member 42, and the window members 58 and 59 is described. The dimensions of the laminate cell 10 can be set, for example, such that the long dimension = 80 mm, the short dimension = 60 mm, and the thickness dimension = 1 mm. In this case, the dimensions of the second support member 42 can be set, for example, such that the long dimension = 100 mm, the short dimension = 40 mm, and the thickness dimension = 10 mm. Moreover, the dimension of each part of the window members 58 and 59 can be set to, for example, a longitudinal dimension = 80 mm, a short dimension = 20 mm, and a thickness dimension = 0.2 mm.

(Presser part)
When holding the laminate cell 10 between the first support member 41 and the second support member 42, the pressing portion 43 presses both the first support member 41 and the second support member 42 so that they are not separated from each other. Is. The pressing portion 43 is located at a portion other than the portion where the X-ray transmission holes 51 and 56 are formed so as not to interfere with the X-rays passing through the X-ray transmission holes 51 and 56 of the first support member 41 and the second support member 42. The first support member 41 and the second support member 42 are pressed in place.

  In the present embodiment, as an example, as shown in FIG. 4, the four corners of the second support member 42 are the pressing portions 43. For example, as shown in FIG. 11, the pressing portion 43 is configured by using a connector composed of a screw 61 and a nut 62. The screw 61 is inserted into a screw mounting hole 52 provided in the first support member 41 and a screw mounting hole 57 provided in the second support member 42 corresponding thereto. The nut 62 is screwed into the male screw portion of the screw 61. When the pressing portion 43 is configured using such a connecting tool, the first support member 41 and the second support member are supported by screwing and tightening the nut 62 to the screw 61 inserted into the screw mounting holes 52 and 57. The members 42 can be pressed so as to be coupled (connected) to each other.

(Procedure for attaching the laminate cell to the sample holder)
Next, a procedure for attaching the laminate cell 10 to the sample holder 31 having the above-described configuration will be described. Here, as an example, a procedure for attaching the laminate cells 10 to the sample holder 31 one by one will be described.

  First, the first support member 41 is supported horizontally with the main surface 48 of the first support member 41 facing upward, and the laminate cell 10 is placed on the main surface 48 of the first support member 41 in this state. At this time, one laminate cell 10 is placed in one sample attachment region 49. Next, the second support member 42 is placed over the laminate cell 10. At this time, if the first support member 41 and the second support member 42 are made of a light transmissive material (typically a transparent material), the laminate cell 10 is interposed between the support members 41 and 42. Even in the state of sandwiching, the positional relationship between the laminate cell 10 and the window members 58 and 59 can be grasped from the outside of the support members 41 and 42. Next, the position of the screw mounting hole 52 of the first support member 41 and the position of the screw mounting hole 57 of the second support member 42 are matched. Thereby, the X-ray transmission hole 51 of the first support member 41 and the X-ray transmission hole 56 of the second support member 42 are arranged substantially coaxially.

  Next, screws 61 and nuts 62 are attached to the four corners of the second support member 42 in order to hold the first support member 41 and the second support member 42 so as not to be separated from each other. Specifically, after inserting the screw 61 from the second support member 42 side into the screw mounting holes 52 and 57 aligned with each other, the nut 62 is screwed into the screw 61. At this time, screws 61 and nuts 62 are respectively attached to the four corners of the second support member 42 and temporarily tightened, and then the four nuts 62 are gradually tightened and finally tightened. 2 The support member 42 can be pressed in a balanced manner with an equal force. The tightening force by the nut 62 is at least strong enough to prevent the laminate cell 10 sandwiched between the first support member 41 and the second support member 42 from falling, and the first support member 41 and the second support member 42. It should be strong enough to prevent distortion.

  When one laminate cell 10 is attached to the first support member 41 by the above procedure, the remaining three laminate cells 10 are attached by the same procedure. Accordingly, as shown in FIG. 4, the laminate cells 10 </ b> A to 10 </ b> D are attached to the first support member 41 in a radial manner using the four second support members 42. Each laminate cell 10 is supported by being sandwiched between a first support member 41 and a second support member 42. At this time, as shown in FIG. 11, the main surface 48 of the first support member 41 is disposed so as to face one main surface of the laminate cell 10, and the main surface 55 of the second support member 42 is laminated. It arrange | positions so that the other main surface of the cell 10 may be opposed. Further, the window member 58 attached to the main surface 48 of the first support member 41 contacts one main surface of the laminate cell 10 and is attached to the main surface 55 of the second support member 42. 59 is in contact with the other main surface of the laminate cell 10.

(Procedure for attaching the sample holder to the holder moving device)
Next, a procedure for attaching the sample holder 31 to the holder moving device 32 will be described. First, the base 47 of the first support member 41 is brought into contact with the rotating plate 34 of the holder moving device 32. At this time, the four connecting holes 54 provided in the base 47 of the first support member 41 are aligned with the four screw holes 36 provided in the rotating plate 34 of the holder moving device 32 correspondingly. To do. Further, the position of the rotation center 35 of the rotating plate 34 and the position of the rotation center 53 set in the base 47 are matched. Next, screws for attaching the holder (not shown) are screwed into the screw holes 36 through the four connecting holes 54, and each screw is gradually tightened. Thereby, the base 47 of the first support member 41 is fixed to the rotating plate 34 of the holder moving device 32. By the above procedure, the sample holder 31 can be attached to the holder moving device 32 as shown in FIG.

  The procedure for attaching the laminate cell 10 to the sample holder 31 or attaching the sample holder 31 to the holder moving device 32 is not limited to the procedure described here. For example, with the second support member 42 attached to the first support member 41, the nut 62 may be loosened moderately to attach or detach the laminate cell 10. Further, the laminate cell 10 may be attached and detached while the sample holder 31 is attached to the rotating plate 34 of the holder moving device 32.

<5. Operation of sample switching device>
Next, the operation of the sample switching device 27 having the above configuration will be described.
First, when the motor of the holder moving device 32 is driven to rotate with the four laminate cells 10 mounted on the sample holder 31, the sample holder 31 rotates integrally with the rotating plate 34 around the rotation centers 35 and 53. Further, when the sample holder 31 rotates, the position of each laminate cell 10 changes in the circumferential direction. For this reason, the laminate cell 10 disposed at the X-ray passage position P (see FIG. 4) can be switched by the rotational movement of the sample holder 31. The X-ray passage position P described here refers to the sample placement portion when the X-rays emitted from the X-ray radiation source 1 in FIG. 1 pass through the sample placement portion 4 via the monochromator 2. 4, the X-ray passing position when the X-ray passes above the pedestal 33 provided in the sample setting section 4, more specifically, as indicated by an arrow in FIG. Say. On the other hand, the rotation axis of the sample holder 31 is arranged in parallel with the optical axis of the X-ray that passes through the sample setting unit 4. The rotation axis of the sample holder 31 is disposed below the optical axis of the X-ray. In the present embodiment, as one preferred embodiment, the rotation axis of the sample holder 31 is set directly below the optical axis of the X-ray. Further, the rotation direction, rotation speed, and rotation amount (rotation angle) of the sample holder 31 depend on the rotation direction, rotation speed, and rotation amount of the motor of the holder moving device 32. Therefore, for example, when a stepping motor is used as the drive source of the holder moving device 32, the rotation direction, rotation speed, and rotation amount of the sample holder 31 are controlled by the order, frequency, and number of drive pulses input to the stepping motor. It becomes possible to do.

  When the sample holder 31 holding the four laminate cells 10 is attached to the rotating plate 34 of the holder moving device 32, the center of gravity of the sample holder 31 is located at a position far away from the rotation center 35. For this reason, we are anxious about the load of the motor of the holder moving apparatus 32 becoming large. In such a case, a weight (not shown) for balancing the mass of the entire holder may be attached to the sample holder 31 as necessary. When this configuration is adopted, the position of the center of gravity of the sample holder 31 can be made closer to the rotation center 35 than when the weight is not attached to the sample holder 31. For this reason, it becomes possible to reduce the load of a motor.

<6. X-ray analysis method>
Next, an X-ray analysis method using the X-ray analysis system according to the embodiment of the present invention will be described. In the present embodiment, as an example of the X-ray analysis method, the laminate cell 10 is charged / discharged under predetermined charge / discharge conditions, and the laminate cell 10 being charged / discharged is irradiated with X-rays to obtain analysis data. An X-ray analysis method for obtaining the above will be described. More specifically, a method for obtaining analysis data (measurement data) related to the X-ray absorbance of the laminate cell 10 during charge / discharge will be described.

(Preparation process)
First, the following work is performed as a preparation process.
That is, the sample holder 31 on which the four laminate cells 10A to 10D are mounted is attached to the rotating plate 34 of the holder moving device 32. The four laminate cells 10A to 10D may be manufactured with different materials (element types and the like) and conditions, or may be manufactured with the same materials and conditions.

  Next, in the sample setting unit 4, the position of the sample holder 31 is adjusted so that X-rays pass through any of the X-ray transmitting holes 51 and 56 of the sample holder 31. The position of the sample holder 31 is adjusted by appropriately rotating the micrometer heads 37 and 38 of the holder moving device 32. Next, as schematically shown in FIG. 12, the four laminate cells 10 </ b> A to 10 </ b> D are electrically connected to the charging / discharging device 26 using connection cables, respectively. At this time, if the first support member 41 and the second support member 42 are each made of an insulating material, the terminal of the connection cord should be connected to the first support member 41 or the second support member 42 during charging / discharging. There is no risk of short-circuiting even when touching.

(Measurement process)
Next, the process shown in FIG. 13 is performed as a measurement process. This processing is executed by the X-ray analysis system 20. In the measurement process, the order of the laminate cells 10 arranged at the X-ray passing position P can be arbitrarily set or changed. Here, as an example, the laminate cell 10 disposed at the X-ray passage position P is in the order of laminate cell 10A → laminate cell 10B → laminate cell 10C → laminate cell 10D → laminate cell 10A →. Shall be switched. Moreover, the operation | movement which switches so that each lamination cell 10A-10D may be arrange | positioned once in the X-ray passage position P is defined as one round of switching operation.

  First, the charging / discharging control unit 28 controls the charging / discharging device 26 to start charging / discharging of the four laminate cells 10A to 10D (step S1). Moreover, the elapsed time after starting charging / discharging of laminate cell 10A-10D is measured, for example with the timer function part (not shown) with which the charging / discharging control part 28 is provided.

  Next, the sample switching control unit 29 operates the sample switching device 27 to place the laminate cell 10A at the X-ray passage position P as shown in FIG. 14 (step S2). When the laminate cell 10A is disposed at the X-ray passage position P, the X-rays pass through the X-ray transmitting holes 51 and 56 of the first support member 41 and the second support member 42 supporting the laminate cell 10A. Become.

  Next, the X-ray control unit 23 operates the monochromator 2 to irradiate the laminate cell 10A with X-rays in a predetermined energy range, and measure the X-ray absorbance of the laminate cell 10A at that time (step S3). . This measurement is the measurement of the first X-ray analysis for the laminate cell 10A arranged at the X-ray passage position P as described above.

Here, the relationship between the energy of X-rays applied to the laminate cell 10 and the measurement of the X-ray absorbance of the laminate cell 10 will be described.
The energy of X-rays irradiated to the laminate cell 10 changes relatively from the low energy side to the high energy side when the X-ray control unit 23 changes the angle of the monochromator 2 under a predetermined condition. . The monochromator 2 takes out X-rays having a specific wavelength (energy) by changing the angle at which X-rays are taken out. For this reason, if the initial angle for extracting the X-rays on the low energy side is the first angle and the final angle for extracting the X-rays on the high energy side is the second angle, the X-ray absorbance of the laminate cell 10 The measurement is performed in the process of changing the angle of the monochromator 2 from the first angle to the second angle. Further, the measurement of the X-ray absorbance of the laminate cell 10 is performed by taking the detection data of the first X-ray detector 3 and the detection data of the second X-ray detector 5 into the measuring instrument 22 and generating the measuring instrument 22. Measurement data and angle data of the monochromator 2 are acquired by the data acquisition unit 24 and stored. Thereby, analytical data (measurement data) indicating X-ray absorbance when X-rays incident on the laminate cell 10 are changed from the low energy side to the high energy side are obtained.

  Next, when the measurement of the X-ray analysis of the laminate cell 10A is completed, the sample switching control unit 29 operates the sample switching device 27 so as to switch the laminate cell 10 disposed at the X-ray passage position P. As shown in FIG. 15, the laminate cell 10B is disposed at the X-ray passage position P (step S4). When the laminate cell 10 disposed at the X-ray passage position P is switched from the laminate cell 10A to the laminate cell 10B, the holder moving device 32 sets the sample holder 31 in one direction in accordance with a control command from the sample switching control unit 29. It is rotated by an angle (40 ° in this embodiment). When the laminate cell 10B is disposed at the X-ray passage position P, the X-ray passes through the X-ray transmitting holes 51 and 56 of the first support member 41 and the second support member 42 supporting the laminate cell 10B. Become.

  Next, the X-ray control unit 23 controls the monochromator 2 to irradiate the laminate cell 10B with X-rays in a predetermined energy range, and measure the X-ray absorbance of the laminate cell 10B at that time (step S5). . This measurement is the measurement of the first X-ray analysis for the laminate cell 10B arranged at the X-ray passage position P as described above.

  Here, the X-ray control unit 23 variably controls the operation conditions (setting values of the first angle and the second angle) of the monochromator 2 for each laminate cell 10 disposed at the X-ray irradiation position P. It is good also as a structure. For example, when the operating conditions of the monochromator 2 applied to the laminate cell 10A and the operating conditions of the monochromator 2 applied to the laminate cell 10B are different from each other, the X-ray control unit 23 is disposed at the X-ray passage position P. It is good also as a structure which can control the monochromator 2 by changing the operating conditions of the monochromator 2 for every laminated cell 10A, 10B. This also applies to the other laminate cells 10C and 10D. When such a configuration is adopted, for example, the positive electrode active materials of the four laminate cells 10A to 10D are made of different materials, thereby changing the operating conditions of the monochromator 2 for each of the laminate cells 10A to 10D. It is possible to respond flexibly when it is necessary to do so.

  Next, when the measurement of the X-ray analysis of the laminate cell 10B is completed, the sample switching control unit 29 operates the sample switching device 27 so as to switch the laminate cell 10 disposed at the X-ray passage position P. As shown in FIG. 16, the laminate cell 10C is disposed at the X-ray passage position P (step S6). When the laminate cell 10 arranged at the X-ray passage position P is switched from the laminate cell 10B to the laminate cell 10C, the holder moving device 32 sets the sample holder 31 in one direction in accordance with a control command from the sample switching control unit 29. It is rotated by an angle (40 ° in this embodiment). When the laminate cell 10C is disposed at the X-ray passage position P, the X-ray passes through the X-ray transmitting holes 51 and 56 of the first support member 41 and the second support member 42 supporting the laminate cell 10C. Become.

  Next, the X-ray control unit 23 controls the monochromator 2 to irradiate the laminate cell 10C with X-rays in a predetermined energy range, and measure the X-ray absorbance of the laminate cell 10C at that time (step S7). . This measurement becomes the measurement of the first X-ray analysis for the laminate cell 10C arranged at the X-ray passage position P as described above.

  Next, when the measurement of the X-ray analysis of the laminate cell 10C is completed, the sample switching control unit 29 operates the sample switching device 27 so as to switch the laminate cell 10 disposed at the X-ray passage position P. As shown in FIG. 17, the laminate cell 10D is disposed at the X-ray passage position P (step S8). When the laminate cell 10 disposed at the X-ray passing position P is switched from the laminate cell 10C to the laminate cell 10D, the holder moving device 32 sets the sample holder 31 in one direction in accordance with a control command from the sample switching control unit 29. It is rotated by an angle (40 ° in this embodiment). When the laminate cell 10D is disposed at the X-ray passage position P, the X-rays pass through the X-ray transmitting holes 51 and 56 of the first support member 41 and the second support member 42 supporting the laminate cell 10D. Become.

  Next, the X-ray control unit 23 controls the monochromator 2 to irradiate the laminate cell 10D with X-rays in a predetermined energy range, and measure the X-ray absorbance of the laminate cell 10D at that time (step S9). . This measurement is the measurement of the first X-ray analysis for the laminate cell 10D arranged at the X-ray passage position P as described above.

  At this stage, all the measurements of the first X-ray analysis are completed for each of the four laminate cells 10A to 10D. In addition, since the measurement of the X-ray analysis is started, one round of switching operation by the sample switching device 27 is performed only once.

  Next, it is determined whether or not the elapsed time from the start of charging / discharging of the four laminate cells 10A to 10D has reached a predetermined charging / discharging test time (predetermined time) (step S10). The charge / discharge control unit 28 measuring the elapsed time determines whether or not the elapsed time since the start of charging / discharging of the four laminate cells 10A to 10D has reached the charge / discharge test time.

  Next, when the charge / discharge control unit 28 determines No in step S10, the sample switching control unit 29 operates the sample switching device 27 to switch the laminate cell 10 disposed at the X-ray passage position P. As in step S2, the laminate cell 10A is placed again at the X-ray passage position P. When the laminate cell 10 disposed at the X-ray passing position P is switched from the laminate cell 10D to the laminate cell 10A, the holder moving device 32 moves the sample holder 31 up to that time according to a control command from the sample switching control unit 29. It is rotated by a predetermined angle (120 ° in this embodiment) in the opposite direction.

  Next, as in step S3, the X-ray controller 23 controls the monochromator 2 to irradiate the laminate cell 10A with X-rays in a predetermined energy range, and the X-ray absorbance of the laminate cell 10A at that time. Measure. This measurement is the second X-ray analysis measurement for the laminate cell 10A rearranged at the X-ray passage position P as described above.

  Next, in order to switch the laminate cell 10 arranged at the X-ray passage position P, the sample switching control unit 29 operates the sample switching device 27, so that the laminate cell 10B is again moved to the X-rays similarly to step S4. Arranged at the passing position P.

  Next, as in step S5, the X-ray controller 23 controls the monochromator 2 to irradiate the laminate cell 10B with X-rays in a predetermined energy range, and the X-ray absorbance of the laminate cell 10B at that time. Measure. This measurement is the measurement of the second X-ray analysis for the laminate cell 10B rearranged at the X-ray passage position P as described above.

  Next, in order to switch the laminate cell 10 disposed at the X-ray passage position P, the sample switching control unit 29 operates the sample switching device 27, so that the laminate cell 10C is again moved to the X-rays similarly to step S6. Arranged at the passing position P.

  Next, as in step S7, the X-ray controller 23 controls the monochromator 2 to irradiate the laminate cell 10C with X-rays in a predetermined energy range, and the X-ray absorbance of the laminate cell 10C at that time. Measure. This measurement is the measurement of the second X-ray analysis for the laminate cell 10C rearranged at the X-ray passage position P as described above.

  Next, in order to switch the laminate cell 10 disposed at the X-ray passage position P, the sample switching control unit 29 operates the sample switching device 27, so that the laminate cell 10D is again moved to the X-rays similarly to step S8. Arranged at the passing position P.

  Next, as in step S9, the X-ray control unit 23 controls the monochromator 2 to irradiate the laminate cell 10D with X-rays in a predetermined energy range, and the X-ray absorbance of the laminate cell 10D at that time. Measure. This measurement is the measurement of the second X-ray analysis for the laminate cell 10D rearranged at the X-ray passage position P as described above.

  At this stage, the measurement of the second X-ray analysis is completed for each of the four laminate cells 10A to 10D. In addition, since the measurement of the X-ray analysis is started, one round of switching operation by the sample switching device 27 is repeated a total of two times.

  Thereafter, the charge / discharge control unit 28 determines that the elapsed time from the start of charging / discharging of the four laminate cells 10A to 10D has reached a predetermined charging / discharging test time (determined as Yes in step S10). Until then, the same processing as above is repeated. When it is determined that the elapsed time has reached the charge / discharge test time, the charge / discharge control unit 28 stops the charge / discharge device 26 and ends the charge / discharge of the four laminate cells 10A to 10D (step S11).

  In the measurement step, the sample switching control unit 29 switches the sample so as to switch the laminate cell 10 arranged at the X-ray passage position P every time one measurement of the X-ray analysis is completed for one laminate cell 10. The device 27 is controlled. Further, the sample switching control unit 29 sets the sample switching device 27 so that the sample switching device 27 repeats at least two times a switching operation of sequentially arranging the four laminate cells 10A to 10D at the X-ray passage position P. Control. In addition, the sample switching control unit 29 arranges each of the four laminate cells 10A to 10D that are being charged / discharged by the charging / discharging device 26 at the X-ray passing position P at least twice within the charging / discharging test time. In addition, the sample switching device 27 is controlled.

According to the above measurement process, for example, the charge / discharge test time per cycle from the start to the end of charge / discharge is 18 hours, and it is necessary to measure the X-ray absorbance of one laminate cell 10 once. Assuming that the time is 4 minutes, a total of 270 analysis data per cycle can be obtained by simple calculation. In addition, in each laminate cell 10A to 10D unit, a total of 67 pieces of analysis data per cycle can be obtained for one laminate cell 10. For this reason, it becomes possible to grasp | ascertain the change of the state in the lamination cell 10 during charging / discharging using corresponding 67 analysis data for every four lamination cells 10A-10D.
When the data acquisition unit 24 is configured by a personal computer, for example, an auxiliary storage device such as a USB (Universal Serial Bus) memory is connected to the personal computer, and the analysis data obtained by the measurement step is You may memorize | store and utilize in this auxiliary storage device.

<7. Effects of the embodiment>
According to the embodiment of the present invention, by repeating the measurement of the X-ray analysis of each of the laminate cells 10A to 10D while switching the laminate cell 10 arranged at the X-ray passage position P by the sample switching device 27, Measurement of four laminate cells 10A to 10D can be performed in parallel within a predetermined charge / discharge test time. For this reason, when compared with the charge / discharge test time per cycle, the analysis data for one laminate cell 10A to 10D can be obtained according to the present embodiment. Data can be obtained simultaneously. Therefore, the X-ray analysis of the four laminate cells 10A to 10D can be performed more efficiently than before. As a result, a few large synchrotron radiation facilities can be used more effectively.

<8. Modified example>
The technical scope of the present invention is not limited to the above-described embodiments, and includes various modifications and improvements as long as the specific effects obtained by the constituent elements of the invention and combinations thereof can be derived.

  For example, in the above embodiment, the X-ray analysis of each of the laminate cells 10A to 10D is performed after the start of charging / discharging of the four laminate cells 10A to 10D. Not exclusively. For example, before starting the charging / discharging of the four laminate cells 10A to 10D, the X-ray analysis of each of the laminate cells 10A to 10D may be performed once. Thereby, after grasping | ascertaining the state of the lamination cells 10A-10D before charging / discharging, it becomes possible to grasp the change of the state of the lamination cells 10A-10D during charging / discharging.

  Moreover, when the charging / discharging control part 28 controls the charging / discharging apparatus 26 and starts charging / discharging of four laminate cells 10A-10D, the timing which starts charging / discharging of each laminate cell 10A-10D is uniformly the same. The timing may be different or may be different from each other. FIG. 18 is a timing chart when charging and discharging of four laminate cells are started simultaneously. In the illustrated timing chart, every time the laminate cell 10 disposed at the X-ray passage position P is switched by the operation of the sample switching device 27, the laminate cell 10 for performing X-ray analysis measurement is sequentially switched.

  On the other hand, FIG. 19 is a timing chart when charging and discharging of the four laminate cells are sequentially started at different timings. In the illustrated timing chart, charging and discharging of the four laminate cells 10A to 10D are started in order in accordance with the order of the laminate cells 10 arranged at the X-ray passage position P. In this case, it is desirable to set a time difference between timings at which charging / discharging of each of the laminate cells 10A to 10D is started in accordance with the time required for one X-ray analysis measurement for one laminate cell 10. For example, when the time required for one X-ray analysis measurement for one laminate cell 10 is 4 minutes, the charging / discharging of the 4 laminate cells 10A to 10D is set to start in order at intervals of 4 minutes. Is preferred. Thus, for example, when the laminate cell 10A and the laminate cell 10B are compared, the time from the start of charge / discharge of the laminate cell 10A until the first measurement of the laminate cell 10A and the charge / discharge of the laminate cell 10B are calculated. The time from the start to the first measurement of the laminate cell 10B can be made uniform. This is the same when compared with other laminate cells 10C and 10D. In addition, the timing which starts charging / discharging of each lamination cell 10A-10D is controlled according to the charging / discharging start command given to the charging / discharging apparatus 26 from the control apparatus 25 (charging / discharging control part 28). There are mainly two specific control modes in that case. In the first control mode, each time the charge / discharge of each of the laminate cells 10A to 10D is started, the measurer operates the control device 25 to give a charge / discharge start command to the charge / discharge device 26. In this mode, the discharge device 26 is controlled. In the second control mode, the charge / discharge control unit 28 automatically controls the charge / discharge device 26 by giving a charge / discharge start command to the charge / discharge device 26 in accordance with a predetermined condition.

  Moreover, in the said embodiment, although the laminate cell 10 is made into the object sample of X-ray analysis, the change of the battery material with time accompanying charging / discharging is measured, but this invention is not limited to this. That is, the present invention is widely used when the state of a sample changes with time due to some external factor, and X-ray analysis is repeatedly performed at least twice per sample in order to examine the process of the change. It is possible to apply.

  Moreover, in the said embodiment, although the structure which switches the lamination cell 10 arrange | positioned in the X-ray passage position P by the rotational movement of the sample holder 31 was illustrated, this invention is not limited to this. For example, although not shown, a configuration may be adopted in which a plurality of laminate cells are arranged and supported on a horizontally long sample holder, and the laminate cells arranged at the X-ray passing position are switched by linear movement of the sample holder. Further, the number of laminate cells that can be simultaneously held by one sample holder is not limited to four, and may be two, three, or five or more, for example.

<9. Other embodiments>
Hereinafter, as another embodiment of the present invention, a case where a sample switching device including a sample holder capable of simultaneously holding more laminate cells is used will be described.

FIG. 20 is a perspective view showing a configuration example of a sample switching device according to another embodiment of the present invention.
In the present embodiment, the configuration of the first support member of the sample holder and the configuration of the holder moving device are particularly different from the above-described embodiment. This will be described in detail below. Note that in this embodiment, description overlapping with the contents described in the above-described embodiment is omitted as much as possible. Therefore, the contents described in the above embodiment are also applied to this embodiment unless otherwise specified.

(Sample holder)
As shown in FIG. 21, the sample holder 100 includes one first support member 101, a maximum of eight (only two of which are shown in FIG. 20) second support members 102, and the first support member 101. And a pressing portion 103 that presses the second support member 102.

(First support member)
FIG. 22 is a perspective view of the first support member. FIG. 23A is a plan view of the first support member, and FIG. 23B is a front view of the first support member.
The first support member 101 is formed in a circular plate shape (disc shape) when viewed from the front. A protrusion 101 </ b> A is provided at the center of the first support member 101. The protruding portion 101 </ b> A is integrally formed with the first support member 101. The protruding portion 101 </ b> A is formed in a state of protruding in the thickness direction of the first support member 101 by having a larger thickness dimension than other portions of the first support member 101. The outer circumferential circle of the first support member 101 and the outer circumferential circle of the protruding portion 101A are concentric circles. Four connecting holes 104 are provided in the protruding portion 101A. These connection holes 104 are for connecting the sample holder 100 to a rotating plate 121 of a holder moving device 120 described later.

  One main surface (hereinafter also simply referred to as “main surface”) 105 of the first support member 101 has a size that allows a maximum of eight laminate cells 10 to be arranged in a plane. The main surface 105 of the first support member 101 is a support surface for supporting the laminate cell 10 with the second support member 102. The above-described protrusion 101 </ b> A protrudes from the main surface opposite to the main surface 105 of the first support member 101. The reason why the protrusion 101A is provided on the first support member 101 is that when the sample holder 100 is attached to a holder moving device 120, which will be described later, and the sample holder 100 is rotated by driving the holder moving device 120, the holder moving device This is to avoid interference (contact) between 120 and the sample holder 100.

  On the main surface 105 of the first support member 101, eight sample attachment regions 106 are virtually partitioned. The eight sample attachment regions 106 are spaced at an appropriate interval between adjacent sample attachment regions 49 so that a maximum of eight laminate cells 10 can be arranged radially on the main surface 105 of the first support member 101. They are arranged radially. Further, between the two sample mounting regions 106 adjacent to each other in the circumferential direction of the first support member 101, a punch hole 109 is provided. The hole 109 is formed so as to penetrate the first support member 101 in the thickness direction. Eight holes 109 are provided side by side in the circumferential direction of the first support member 101. In addition, the holes 109 are provided radially in the circumferential direction of the first support member 101. Each punch hole 109 is formed in a substantially triangular shape when viewed from the front. The two side portions of the punch hole 109 are formed so as to be adjacent to the long side portions of the two sample attachment regions 106 on both sides adjacent to each other in the circumferential direction of the first support member 101.

  Each sample attachment region 106 is provided with one X-ray transmission hole 107 and four screw attachment holes 108. A total of eight X-ray transmitting holes 107 are provided for the entire first support member 101 in accordance with the number of laminate cells 10 that can be held by one sample holder 100. A rotation center 110 of the sample holder 100 is set at the center of the protrusion 101 </ b> A of the first support member 101. The four connecting holes 104 described above are provided around the rotation center 110 in the protruding portion 101A. In the radial direction of the first support member 101, eight X-ray transmission holes 107 are formed at the same distance from the rotation center 110 (on the same circumference). Further, in the circumferential direction of the first support member 101, eight X-ray transmission holes 107 are formed with an equal angular interval θ2 (in the present embodiment, θ2 = 45 ° interval) (FIG. 23 ( See B)).

(Second support member)
The second support member 102 includes a support surface (not shown) for supporting the laminate 10 with the first support member 101, one X-ray transmitting hole 112, and four screw mounting holes 113. And have. The second support member 102 basically has the same configuration as that of the above-described embodiment (second support member 42 shown in FIG. 8).

  Although not shown, a window member is attached to the main surface 105 of the first support member 101, and a window member is also attached to a support surface (not shown) of the second support member 102.

(Holder moving device)
The holder moving device 120 is mounted on a pedestal 33 provided in the sample setting unit 4 of the X-ray analyzer described above. The holder moving device 120 includes a motor (not shown), a rotating plate 121 that rotates using the motor as a drive source, and a stage mechanism 122 that supports the rotating plate 121 so as to be movable. A screw hole (not shown) for attaching the sample holder 100 is provided on the front surface of the rotating plate 121.

  The stage mechanism 122 includes an upper stage 123, a lower stage 124, and a plurality (four in the illustrated example) of rods 125 that connect the upper stage 123 and the lower stage 124. The upper stage 123 is mounted on the upper end portion of the rod 125. The rod 125 is provided to stand vertically from the lower stage 124. The upper stage 123 moves the rotating plate 121 in the vertical direction according to the rotation of the micrometer head 126, and the lower stage 124 moves the rotating plate 121 in the horizontal direction according to the rotation of the micrometer head 127. For this reason, it is possible to independently adjust the position of the rotating plate 121 in the vertical direction and the horizontal direction by appropriately rotating the micrometer heads 126 and 127.

  The rotation center 110 of the sample holder 100 is set immediately above the X-ray passage position P (see FIGS. 20 and 21). The X-ray passage position P is set as follows so that the X-ray passing right below the rotation center 110 does not interfere with the stage mechanism 122. That is, the X-ray passing position P is set between two rods 125 adjacent in the horizontal direction (intermediate position) when the sample holder 100 is viewed from the front.

(Installation procedure)
When attaching the laminate cell 10 to the sample holder 100, the laminate cell 10 is placed in any one of the sample attachment regions 106 with the main surface 105 of the first support member 101 facing upward. Next, the second support member 102 is placed over the laminate cell 10. Next, the first support member 101 and the second support member 102 are pressed by the pressing portion 103. By repeating such attachment work, a maximum of eight laminate cells 10 can be attached to one sample holder 100.

  When attaching the sample holder 100 to the holder moving device 120, the protrusion 101 </ b> A of the first support member 101 is fixed to the rotating plate 121 of the holder moving device 120. Specifically, the four connecting holes 104 provided in the protruding portion 101A are aligned with the four screw holes (not shown) provided in the rotating plate 121 of the holder moving device 120, and in this state A screw for attaching the holder (not shown) is screwed into the screw hole and tightened. As a result, the protrusion 101 </ b> A of the first support member 101 is fixed to the rotating plate 121 of the holder moving device 120.

(Operation of sample switching device)
When the motor of the holder moving device 120 is driven to rotate with the eight laminate cells 10 mounted on the sample holder 100, the sample holder 100 rotates integrally with the rotating plate 121 around the rotation center 110. Further, when the sample holder 100 rotates, the position of each laminate cell 10 changes in the circumferential direction. For this reason, the laminate cell 10 disposed at the X-ray passage position P (FIGS. 20 and 21) can be switched by the rotational movement of the sample holder 100.

(X-ray analysis method)
When the measurement process in the X-ray analysis method described above is performed using the sample switching device having the above-described configuration, the sample switching control unit 28 controls the operation of the sample switching device as follows, so that the X-ray passage position is as follows. The laminate cells 10 arranged in P are sequentially switched.
Here, for convenience of explanation, the eight laminated cells 10 attached to the sample holder 100 are distinguished by reference numerals 10-1 to 10-8 in the order in which the first support members 101 are arranged in the circumferential direction. And in the said measurement process, the lamination cell 10 arrange | positioned in the passage position P of X-ray is laminated cell 10-1-> lamination cell 10-2-> lamination cell 10-3-> lamination cell 10-4-> lamination cell 10-5. → Lamination cell 10-6 → Lamination cell 10-7 → Lamination cell 10-8 → Lamination cell 10-1 →...

  In such a case, the sample switching control unit 28 first places the laminate cell 10-1 at the X-ray passage position P. Next, when the measurement of the X-ray analysis of the laminate cell 10-1 is completed, the sample switching control unit 28 drives the holder moving device 120 to move the sample holder 100 in one direction at a predetermined angle (45 ° in this embodiment). Just rotate. Thereby, the laminate cell 10 arrange | positioned in the X-ray passage position P switches from the laminate cell 10-1 to the laminate cell 10-2.

  Next, when the measurement of the X-ray analysis of the laminate cell 10-2 is completed, the sample switching control unit 28 drives the holder moving device 120 to move the sample holder 100 in one direction at a predetermined angle (45 ° in this embodiment). Just rotate. Thereby, the laminate cell 10 arrange | positioned in the X-ray passage position P switches from the laminate cell 10-2 to the laminate cell 10-3.

  Thereafter, the sample switching control unit 28 controls the laminate cell 10 to be arranged at the X-ray passing position P by the same control as described above, as follows: laminate cell 10-4 → laminate cell 10-5 → laminate cell 10-6 → laminate cell 10 -7 → Laminate cell 10-8.

  Next, when the measurement of the X-ray analysis of the laminate cell 10-8 is completed, the sample switching control unit 28 drives the holder moving device 120 to move the sample holder 100 to a predetermined angle in the opposite direction (this embodiment). 315 °). Thereby, the laminate cell 10 arrange | positioned in the X-ray passage position P switches from the laminate cell 10-8 to the laminate cell 10-1. Thereafter, the same operation is repeated until the elapsed time from the start of charging / discharging of the laminate cells 10A to 10D reaches a predetermined charging / discharging test time.

  When the sample switching device is used, since eight laminate cells 10 can be held in one sample holder 100, measurement of the eight laminate cells 10 is performed in parallel within a predetermined charge / discharge test time. Can be done. Therefore, the X-ray analysis of the laminate cell 10 can be performed more efficiently.

  When actually performing X-ray analysis using a sample switching device, it is not always necessary to attach the largest number of laminate cells to the sample holder. You may measure by attaching to.

DESCRIPTION OF SYMBOLS 1 ... X-ray radiation light source 2 ... Monochromator 3 ... 1st X-ray detector 4 ... Sample installation part 5 ... 2nd X-ray detector 10 ... Laminate cell (sample)
DESCRIPTION OF SYMBOLS 11 ... Positive electrode 12 ... Negative electrode 13 ... Separator 14 ... Battery element 20 ... System for X-ray analysis 25 ... Control device 26 ... Charge / discharge device 27 ... Sample switching device 28 ... Charge / discharge control unit 29 ... Sample switching control unit 31, 100 ... Sample holder 32, 120 ... Holder moving device

Claims (5)

An in-situ X-ray that obtains analytical data by irradiating the laminated cell with X-rays using a laminated cell in which a battery element formed by laminating a positive electrode and a negative electrode with a separator interposed therebetween is sealed with a laminate film together with an electrolytic solution. An X-ray analysis system used for analysis,
A sample having a sample holder capable of holding a plurality of laminate cells, and of the plurality of laminate cells held by the sample holder, the laminate cell arranged at the X-ray passing position is switched by moving the sample holder. A switching device;
A charge / discharge device for charging / discharging the plurality of laminate cells held by the sample holder within a predetermined charge / discharge test time;
A control device for controlling the sample switching device and the charge / discharge device so as to perform X-ray analysis measurements of the plurality of laminate cells in parallel within the charge / discharge test time;
An X-ray analysis system comprising: The control device drives the sample switching device to switch the laminate cell to be arranged at the X-ray passing position each time measurement of one X-ray analysis is completed for one laminate cell, and The sample switching device is controlled so that the sample switching device repeats at least two times or more within the charge / discharge test time in order to sequentially arrange the laminate cells at the X-ray passage positions. The system for X-ray analysis according to claim 1. The said control apparatus controls the said charging / discharging apparatus so that the charging / discharging of these lamination cells may be started in order according to the order of the lamination cell arrange | positioned in the passage position of the said X-ray. The system for X-ray analysis according to 1 or 2. The said control apparatus controls the operation | movement of the said sample switching apparatus so that it may interlock | cooperate with the operation | movement of the monochromator which adjusts the energy of the X-ray irradiated to the said lamination cell. The system for X-ray analysis described in 1. An in-situ X-ray that obtains analytical data by irradiating the laminated cell with X-rays using a laminated cell in which a battery element formed by laminating a positive electrode and a negative electrode with a separator interposed therebetween is sealed with a laminate film together with an electrolytic solution. A program used for an X-ray analysis system used for analysis,
A sample having a sample holder capable of holding a plurality of laminate cells, and of the plurality of laminate cells held by the sample holder, the laminate cell arranged at the X-ray passing position is switched by moving the sample holder. A switching device;
A charge / discharge device that charges and discharges the plurality of laminate cells held by the sample holder within a predetermined charge / discharge test time, and is subject to control,
A program for causing a computer to function as a control device that controls the sample switching device and the charge / discharge device so that X-ray analysis measurements of the plurality of laminate cells are performed in parallel within the charge / discharge test time.

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