JP6377008B2 - Sample stage for observation - Google Patents

Description

  The present invention relates to an observation sample stage, and for example, relates to an observation sample stage for mounting an observation device such as an electron microscope.

  In recent years, lithium ion secondary batteries are highly expected to be used as mobile batteries because of their high capacity and high energy density. These batteries have a positive electrode plate and a negative electrode plate, and a separator disposed between the positive electrode plate and the negative electrode plate.

  Usually, the positive electrode plate and the negative electrode plate are formed by mixing a paint (positive electrode paint or negative electrode paint) prepared by mixing an active material (positive electrode active material or negative electrode active material), a conductive additive, a binder, and a solvent on a current collector. It is applied to and dried. In order to improve the discharge capacity of the lithium ion secondary battery, the positive electrode plate and the negative electrode plate are generally rolled to increase the density of the active material. The capacity of the lithium ion secondary battery increases as the density of the active material in the electrode plate increases.

  However, the lithium ion secondary battery has a problem that the active material repeatedly expands and contracts during charge and discharge, so that the electrode plate is deformed (buckled) and the cycle life is reduced. It is important to observe the change in state of the electrode plate during charging and discharging and the behavior of lithium ions with respect to the electrode plate in order to improve the capacity and life of the lithium ion secondary battery.

  As the above observation means, in Patent Document 1, the electrode surface is excavated in the thickness direction by irradiation with an ion beam, and a scanning ion microscope (SIM) image of the active material layer on the excavated surface is observed, and the observed SIM image A method for evaluating the performance of the electrode based on the contrast of the active material in the above has been proposed.

  Patent Document 2 discloses a sample stage for microscope observation that can be carried out on the spot together with energization of an electronic material and observation during energization of the electronic material.

  Non-Patent Document 1 describes that a change in volume expansion of the Si negative electrode of an all-solid-state lithium ion battery can be visually captured by an in-situ observation method using a scanning electron microscope (SEM). Has been. Furthermore, it has been clarified that the active material expands with time when the battery is charged.

JP 2007-123207 A JP2013-122893A

Yoshinori Okamoto et al., “Investigation of Li ion storage mechanism in all-solid-state Li-ion battery using in-situ SEM observation method”, The Japanese Society of Microscopy 70th Memorial Lecture, May 11-13, 2014 12 pmB_SM4-09

  Based on the above, it is considered that the compressive force acting on the battery and the electrical state value of the battery change over time during charging, and these may be deeply involved in the deterioration phenomenon of the battery. High nature. Here, examples of the electrical state value of the battery include a voltage value, a current value, and a resistance value. However, in the conventional apparatus, there is no observation sample stage provided with means for measuring and recording the compressive force acting on the battery that is being energized (charging and discharging) and the electrical state value of the battery that is being energized. Therefore, there has been no means for examining in detail the relationship between the compressive force acting on the energized battery, the electrical state value of the energized battery, and the deterioration phenomenon of the battery. In addition, although the sample stand for microscope observation of the patent document 2 mentioned above can observe the electronic material in energization with a microscope, it does not have a means for measuring the compressive force and the electrical state value acting on the electronic material. It was.

  This invention is made | formed in view of the above situations, and the objective of this invention is providing the sample stand for observation which can measure the compressive force which acts on the electronic material during electricity supply.

The above object of the present invention is achieved by the following configurations.
(1) An observation sample stage for attaching an observation device for supplying an electric current to an electronic material placed in a closed space and observing a change with time of the electronic material,
An electronic material holding mechanism for holding the electronic material;
Current supply means for supplying current to the electronic material;
Switching means for turning on and off the current supply from the current supply means;
Control means for controlling the current from the current supply means;
A mounting portion for mounting the observation device;
Compressive force measuring means for measuring the compressive force acting on the electronic material being energized;
A sample stage for observation characterized by comprising:
(2) The observation sample stage according to (1), further comprising: an electrical state value measuring unit that measures an electrical state value of the electronic material during energization.
(3) For observation according to (2), comprising recording means for recording at least one of a compressive force acting on the electronic material being energized and an electrical state value of the electronic material being energized Sample stage.
(4) The observation sample stage according to (3), wherein the recording means is disposed in the closed space.
(5) The observation sample stage according to (3), wherein a space different from the closed space is formed, and the recording unit is disposed in the space.
(6) The observation sample stage according to any one of (1) to (5), wherein the electronic material is a secondary battery.

  According to the observation sample stage according to the present invention, means for energizing the electronic material (current supply means, switching means, control means), and compressive force measuring means for measuring the compressive force acting on the energized electronic material; Therefore, it is possible to measure the compressive force acting on the energized electronic material at the same time as supplying an electric current to the electronic material.

It is sectional drawing which shows the whole structure of the sample stand for microscope observation which concerns on one Embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

1. 1. Configuration of Microscope Observation Sample Stand FIG. 1 is a sectional view showing a microscope observation sample stand according to the embodiment.

  In FIG. 1, a secondary battery, more specifically, a processed all solid state battery, is used as the electronic material S to be observed. However, a chemical battery such as a primary battery or a fuel cell may be used. Alternatively, a capacitor, a piezo element, or the like may be employed. In the microscope observation sample stage 1 according to the present embodiment, the electronic material S is observed with a microscope, the compression force acting on the electronic material S is measured while the electronic material S is energized, and the electronic material S Measurement of the electrical state value can be performed.

  In FIG. 1, a microscope observation sample stage 1 is fitted into a housing 3 having an inverted U-shaped cross section having a recess 3 a formed on the lower surface and a recess 3 a of the housing 3 as an outer component, and a recess 2 a is formed on the lower surface. The base 2 formed, a base lower member 5 attached to the lower surface of the base 2 so as to close the recess 2a, a base material 16 that supports the base lower member 5 from below, and an upper surface of the housing 3 are not shown. And an attachment portion 4 to which an electron microscope such as a scanning electron microscope (SEM) can be attached.

  Further, the microscope observation sample stage 1 includes two small batteries 6a and 6b (current supply means) for supplying current to the electronic material S, and a micro switch 7 (switching) for turning on / off current from the small batteries 6a and 6b. Means), an electronic material holding mechanism 8 for holding the electronic material S, and a constant current diode 9 constituting a constant current circuit (control means) for controlling the current from the small batteries 6a and 6b. . As the small batteries 6a and 6b, for example, a commercially available button-type lithium battery (3V) can be used. Among these, the small batteries 6a and 6b are disposed in a space SP2 described later, and the microswitch 7, the electronic material holding mechanism 8, and the constant current diode 9 are disposed in a closed space SP1 described later.

The housing 3 forms a closed space SP1 in the recess 3a by attaching the base 2 to the lower part of the recess 3a. An O-ring 10 is disposed as a sealing material between the outer side wall of the base 2 and the inner side wall of the recess 3a of the housing 3 to enhance the sealing performance of the closed space SP1. The closed space SP1 is a vacuum space (10 ⁻⁶ Pa to 1000 Pa) whose degree of vacuum is increased by a vacuum pump or the like. The closed space SP1 may be a space filled with an inert gas (such as argon gas or nitrogen gas) atmosphere.

  An observation device such as an electron microscope (not shown) can be connected to the mounting portion 4 provided above the central portion of the housing 3. The housing 3 is provided with a communication hole 3b that allows the attachment portion 4 and the closed space SP1 to communicate with each other. Therefore, the electronic material S arranged in the closed space SP1 can be observed through the communication hole 3b by the electron microscope connected to the attachment portion 4.

  The base lower member 5 disposed on the lower surface of the base 2 closes the recess 2a and forms a space SP2. An O-ring 11 as a sealing material is disposed between the lower surface of the base 2 and the upper surface of the base lower member 5, and the sealing performance of the space SP2 is maintained.

  In the space SP2, two small batteries 6a and 6b are provided, and the positive electrode of the small battery 6a and the negative electrode of the small battery 6b are in contact with each other. As described above, by disposing the small batteries 6a and 6b in the space SP2 different from the closed space SP1, the failure of the small batteries 6a and 6b can be prevented. If the small batteries 6a and 6b are arranged in the closed space SP1 that is a vacuum space, the possibility that the small batteries 6a and 6b break down increases.

  The plus electrode of the small battery 6b is electrically connected to the microswitch 7 in the closed space SP1 through the conductive member 12. The micro switch 7 is provided with a cap 7a serving as a charge / discharge trigger. A pulling member 13 communicating with the outside of the microscope observation sample stage 1 is attached to the cap 7a. The operator can remove the cap 7 a from the microswitch 7 by pulling the pulling member 13, and can start charging and discharging the electronic material S.

  The electronic material holding mechanism 8 includes first and second contact members 8a and 8b and first and second contact members 8a and 8b that contact the front and back surfaces (left and right surfaces in the drawing) of the electronic material S. Via the first and second holding members 8c, 8d holding the electronic material S, the pressurizing means 8g for pressurizing the electronic material S by bringing the pressing member 8e into contact with the second holding member 8d, and a load cell described later And a supporting means 8h for supporting the electronic material S pressurized through 8i on the side opposite to the pressing means 8g.

  The first and second contact members 8a and 8b are made of, for example, a metal foil such as copper or indium, and cover the entire surface of the electronic material S and the back surface. Thereby, the 1st and 2nd contact members 8a and 8b function as a means for pressurizing the electronic material S uniformly. The first and second holding members 8c and 8d are made of a conductive material such as stainless steel, for example, and sandwich the electronic material S via the first and second contact members 8a and 8b. The first and second contact members 8a and 8b and the first and second holding members 8c and 8d function as members that receive current and voltage in order to charge and discharge the electronic material S.

  The pressing means 8g includes a pressing member 8e made of a metal screw or the like, and a base 8f having a screw hole into which the pressing member 8e is screwed. Since the pressing member 8e is longer than the screw hole of the base 8f, it can come into contact with the second holding member 8d while being screwed into the screw hole. And the holding force with respect to the electronic material S can be changed by adjusting the pressing force with respect to the 2nd holding member 8d. In addition, you may employ | adopt a metal spring as the pushing member 8e.

  The push member 8e and the microswitch 7 are electrically connected by a lead wire 15 and a constant current diode 9 is inserted in the middle of the lead wire 15. Note that the microswitch 7 may be provided outside the closed space SP1.

  The support means 8h supports the electronic material S via the first contact member 8a, the first holding member 8c, and the load cell 8i. That is, the load cell 8i is disposed between the first holding member 8c and the support means 8h. Here, when the electronic material S is a secondary battery in particular, the active material repeats expansion and contraction over time during energization (during charging and discharging). A compressive force acts on S from the first and second contact members 8a and 8b. Since the expansion force from the electronic material S also acts on the load cell 8i via the first contact member 8a and the first holding member 8c, the load cell 8i acts on the electronic material S by measuring the expansion force. It is possible to detect the compression force. In this way, the load cell 8i is configured as a compressive force measuring unit that measures the compressive force acting on the electronic material S being energized. In the load cell 8i of the present embodiment, the diameter (vertical width) of the portion adjacent to the first holding member 8c is set smaller than the diameter of the other portions. Thereby, the one-sided contact of the load cell 8i with respect to the 1st holding member 8c can be suppressed.

  The microscope observation sample stage 1 includes an electrical state value measuring unit (not shown) that measures an electrical state value (for example, a voltage value, a current value, and a resistance value) of the electronic material S being energized. As described above, the compressive force acting on the electronic material S measured by the load cell 8i and the electrical state value of the electronic material S measured by the electrical state value measuring unit are recorded by a conductive member or the like (not shown). 17 is transmitted.

  The recording unit 17 includes, for example, a USB type data logger, and records data transmitted from the load cell 8i or the electrical state value measuring unit. In order to read the data recorded in the recording means 17, the recording means 17 is taken out of the microscope observation sample stage 1 and connected to a personal computer or the like.

  As described above, according to this embodiment, the current is supplied to the electronic material S, and at the same time, the compressive force acting on the energized electronic material S and the electrical state value of the electronic material S can be measured and recorded. it can. Therefore, the relationship between the compressive force acting on the electronic material S or the electrical state value of the electronic material S and the deterioration phenomenon of the electronic material S can be clarified, and the life extension of the electronic material S is satisfied. It becomes possible.

  In FIG. 1, the recording means 17 is arranged in the closed space SP1, but it may be arranged in the space SP2. For example, when the recording means 17 is arranged in the closed space SP1, the arrangement space is wide, but the exposure amount of electron beams, X-rays, etc. by the electron microscope increases. When this arrangement is adopted, when the electronic material S is taken out, such as when the electronic material S is exchanged, the recording means 17 has only to be taken out, so that the working efficiency is high. When the recording means 17 is arranged in the space SP2, the arrangement space is narrow, but the exposure amount of electron beams, X-rays, etc. by an electron microscope can be reduced.

2. Regarding the observation at the time of energization and the measurement of the compressive force and the electrical state value In the above configuration, the operator first holds the electronic material S by the electronic material holding mechanism 8. In this case, the holding force by the pressurizing means 8g, that is, the pressing force against the electronic material S is adjusted by the value detected by the load cell 8i.

  Subsequently, the operator removes the cap 7 a of the micro switch 7 by pulling the pulling member 13. Then, current is supplied to the electronic material S from the small batteries 6a and 6b through the conductive member 12, the lead wire 15, the constant current diode 9, and the pressing member 8e. That is, in this embodiment, charging of the electronic material S that is an all-solid battery is started. Specifically, a constant current can be supplied to the electronic material S for a predetermined time, and after the predetermined time has elapsed, the current can be supplied so as to decrease the current value downward. The constant current can be varied by the constant current diode 9.

  As described above, according to the microscope observation sample stage 1, since the electronic material S is provided with the means for energizing the electronic material S and the mounting portion 4 to which the electronic microscope is attached, the electronic material S is simultaneously scanned while being charged. The electronic material S can be observed with a scanning electron microscope or the like. In this way, it is possible to easily observe the structural change during charging of the electronic material S on the spot while charging the electronic material S. Further, since the microscope observation sample stage 1 includes the load cell 8i, the electrical state value measuring means, and the recording means 17, the measurement of the compressive force acting on the electronic material S in a state where the electronic material S is energized. And recording, and measurement and recording of electrical state values of the electronic material S can be performed. In particular, in this embodiment, since the means for energizing the electronic material S, the load cell 8i, the electrical state value measuring means, the recording means 17 and the like are integrally configured, complicated work such as connection is not required. , Work efficiency can be improved.

  In addition, it is not restricted at the time of charge of the electronic material S, Even when the electronic material S is discharged, the electronic material S is observed with a microscope, the compression force acting on the electronic material S is measured and recorded, and the electrical state of the electronic material S Values can be measured and recorded. In this case, instead of the constant current diode 9, a constant current diode in which a current flows in the opposite direction is attached, and a metal dummy block is brought into contact with the conductive member 12 instead of the small batteries 6a and 6b. Thus, the electronic material S can be discharged.

  In the above embodiment, an electron microscope such as a scanning electron microscope (SEM) is employed as an observation apparatus that is attached to the attachment portion 4 and observes the temporal change of the electronic material S, but is not limited thereto. Rather, Auger electron spectrometer (AES), electron energy loss spectrometer (EELS), energy dispersive X-ray fluorescence spectrometer (EDX), electron microanalyzer (EPMA), X-ray photoelectron spectrometer (XPS), two Other observation devices such as a secondary ion mass spectrometer (SIMS), a Fourier transform infrared spectrometer (FTIR), or a Raman spectrometer can also be employed.

  Moreover, in the said embodiment, although the small batteries 6a and 6b were used as an electric current supply means, it is not limited to this, For example, you may use the direct current power source which converted household power supply with the converter as an electric current supply means. .

  The above is a mode for carrying out the present invention. However, the present invention is not limited by the above embodiment as a matter of course, and it is needless to say that the present invention can be carried out with appropriate modifications within a range that can meet the gist of the present invention. All of these are possible within the scope of the present invention.

DESCRIPTION OF SYMBOLS 1 Microscope observation sample base 2 Base 2a Recessed part 3 Housing 3a Recessed part 4 Mounting part 5 Base lower member 6a, 6b Small battery (current supply means)
7 Micro switch (switching means)
8 Electronic material holding mechanism 8a, 8b Abutting member 8c, 8d Holding member 8e Pushing member 8g Pressurizing means 8h Supporting means 8i Load cell (compressive force measuring means)
9 the constant current diode 10, 11 O-ring 12 conductive member 13 pulling member
1 5 Lead wire 16 Base material 17 Recording means S Electronic material SP1 Closed space SP2 Space

Claims (3)

An observation sample stage for attaching an observation device for supplying an electric current to an electronic material placed in a closed space and observing a change with time of the electronic material,
An electronic material holding mechanism for holding the electronic material;
Current supply means for supplying current to the electronic material;
Switching means for turning on and off the current supply from the current supply means;
Control means for controlling the current from the current supply means;
A mounting portion for mounting the observation device;
Compressive force measuring means for measuring the compressive force acting on the electronic material being energized;
An electrical state value measuring means for measuring an electrical state value of the electronic material being energized;
A recording means that is disposed in the closed space and records at least one of a compressive force acting on the electronic material being energized and an electrical state value of the electronic material being energized;
A sample stage for observation characterized by comprising: A view in which a current is supplied to an electronic material placed in a closed space to observe the temporal change of the electronic material.
An observation sample stage for mounting the observation device,
An electronic material holding mechanism for holding the electronic material;
Current supply means for supplying current to the electronic material;
Switching means for turning on and off the current supply from the current supply means;
Control means for controlling the current from the current supply means;
A mounting portion for mounting the observation device;
Compressive force measuring means for measuring the compressive force acting on the electronic material being energized ;
An electrical state value measuring means for measuring an electrical state value of the electronic material being energized ;
A recording that is arranged in a space formed separately from the closed space and records at least one of a compressive force acting on the electronic material being energized and an electrical state value of the electronic material being energized Means,
A sample stage for observation characterized by comprising: The observation sample stage according to claim 1 or 2, wherein the electronic material is a secondary battery .

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