JP6943811B2 - Ion behavior detector, secondary battery device and scanning probe microscope - Google Patents

Description

The present invention relates to an ion behavior detection device, a secondary battery device, and a scanning probe microscope.

Conventionally, the AC impedance method has been used as a simple method for measuring the internal resistance of a battery. For example, in a commercially available internal resistance measuring device, an AC voltage of 1 kHz is applied between the positive and negative electrodes, and the resistance is measured as the internal resistance.

However, the internal resistance measured by the above method is mainly the total value of the electron conduction resistance and the ionic conduction resistance in the electrode mixture layer and the ionic conduction resistance in the separator layer, so it is difficult to detect each of them. Is. Electron conduction resistance and ion conduction resistance have a great influence on battery performance. If the ionic conduction resistance can be detected independently, the electron conduction resistance can also be obtained from the total value. Therefore, it is desired to establish a method for detecting the ionic conduction resistance alone.

On the other hand, as a method for mapping the electrochemical activity on the surface of the material, there are a step of applying an electrical excitation signal to the material and a step of inducing the movement of movable ions of the material in response to the electrical excitation signal. , A method has been proposed comprising the step of measuring the electrochemical strain response induced by the movement of mobile ions (see, for example, Patent Document 1). According to this method, it is possible to evaluate the local ionic properties of the material.

Japanese Patent Application Laid-Open No. 2014-502354

However, even with the method of Patent Document 1, it is not possible to accurately detect ionic behavior such as ionic conduction resistance in a detection object such as an electrode layer of a battery or a (solid) electrolyte layer.

The present invention has been made in view of the above, and an object of the present invention is to provide an ion behavior detection device capable of accurately detecting the behavior of ions in a detection object.

(1) The present invention is an ion behavior detection device that detects the behavior of ions in a detection target, and has a detector having at least one detector arranged in contact or non-contact with the detection target. The detector includes a control unit that controls the detection unit, and the detector has an ion absorption / release substance composed of a metal layer having a metal layer and an ion absorption / release substance that absorbs and releases ions in order from the inside at least at the tip portion. The detection unit includes a layer and a solid electrolyte layer composed of a solid electrolyte, and the detection unit is controlled by the control unit to move an ion from the detection object to the tip portion, and / or Provided is an ion behavior detection device that detects the behavior of ions in the detection target by detecting a value correlating with the state of ions in the detection target between the detection target and the tip portion. ..

(2) In the ion behavior detection device of (1), the detection target is an electrode layer or a solid electrolyte layer of a secondary battery, and the detection unit has at least two detectors and the control unit. Controlled by Is preferable.

(3) In the ion behavior detection device of (2), the detection unit is controlled by the control unit, and at least one of the detectors moves along the plane direction of the electrode layer or the solid electrolyte layer. , It is preferable to detect the behavior of ions in the electrode layer or the solid electrolyte layer.

(4) In the ion behavior detection device of (1), the detection target is an electrode layer or a solid electrolyte layer of a secondary battery, and the detection unit further has at least one current collector and controls the control. At least one tip of the detector is arranged on the surface, near or inside the surface of the electrode layer or the solid electrolyte layer, and at least one of the current collectors is the electrode layer or the solid electrolyte. It is preferable to detect the behavior of ions in the electrode layer or the solid electrolyte layer in contact with the layer.

(5) In the ion behavior detection device of (4), the detection unit is controlled by the control unit, and at least one tip of the detector is arranged on or near the surface of the electrode layer or the solid electrolyte layer. It is preferable to detect the behavior of ions in the electrode layer or the solid electrolyte layer in a state where at least one of the current collectors is inserted inside the electrode layer or the solid electrolyte layer.

(6) The present invention includes any of the ion behavior detection devices (1) to (5) and a secondary battery control unit that controls charging, discharging, and temperature of the secondary battery, and the detection target is , The electrode layer or the solid electrolyte layer of the secondary battery, and the secondary battery control unit charges the secondary battery based on the behavior of ions in the electrode layer or the solid electrolyte layer detected by the detection unit. , Provide a secondary battery device that controls discharge and temperature.

(7) The present invention provides a scanning probe microscope comprising any of the ion behavior detection devices (1) to (5), wherein the detector is a cantilever whose tip is composed of a probe. ..

According to the present invention, it is possible to provide an ion behavior detection device capable of accurately detecting the behavior of ions in a detection object.

Further, for example, in a scanning probe microscope or the like, the state of the sample surface is observed by measuring the current flowing between the probe and the sample and the atomic force, but according to the ion behavior detection device of the present invention, ions are observed. The behavior (state) of (cations and anions) can be detected in a non-solution environment. In addition, when measuring the electrochemical reaction, it was necessary to use an electrolytic solution in which charged particles can move. However, according to the present invention, since no electrolytic solution is used, even in a solid state. The behavior (state) of ions can be detected.

Further, according to the present invention, if the measurement is performed while controlling the position of the detector, for example, the voltage and current distribution of a minute portion can be measured with high accuracy together with the position information. Therefore, for example, it is possible to measure the voltage and current distribution of the electrode layer (positive electrode layer, negative electrode layer) and solid electrolyte layer of a solid secondary battery and detect the state and resistance of internal ions (charged particles) with high accuracy. Therefore, by feeding back these detection results to voltage, current, temperature control, etc., the performance and durability of the solid-state secondary battery can be improved. That is, according to the present invention, the deteriorated state of the battery, which was conventionally determined only by the voltage, can be directly detected as the deteriorated state of the electrode (active material) and the solid electrolyte. Deterioration suppression control is possible.

It is a figure which shows the structure of the ion behavior detection apparatus which concerns on one Embodiment of this invention, and is the figure which shows the state which the detector is in contact with the surface of the detection object. It is a figure which shows the structure of the ion behavior detection apparatus which concerns on one Embodiment of this invention, and is the figure which shows the state which the detector is arranged near the surface of the detection object. It is a figure which shows the structure of the ion behavior detection apparatus which concerns on the modification 1 of one Embodiment of this invention. It is a figure which shows the structure of the ion behavior detection apparatus which concerns on the modification 2 of one Embodiment of this invention. It is a figure which shows the measurement example 1 of the ion behavior detection apparatus which concerns on one Embodiment of this invention. It is a figure which shows the measurement example 2 of the ion behavior detection apparatus which concerns on one Embodiment of this invention. It is a figure which shows the measurement example 3 of the ion behavior detection apparatus which concerns on one Embodiment of this invention. It is a figure which shows the measurement example 4 of the ion behavior detection apparatus which concerns on one Embodiment of this invention. It is a figure which shows the measurement example 5 of the ion behavior detection apparatus which concerns on one Embodiment of this invention. It is a figure which shows the measurement example 6 of the ion behavior detection apparatus which concerns on one Embodiment of this invention. It is a figure which shows the measurement example 7 of the ion behavior detection apparatus which concerns on one Embodiment of this invention. It is a figure which shows the measurement example 8 of the ion behavior detection apparatus which concerns on one Embodiment of this invention. It is a figure which shows the structure of the secondary battery device which concerns on one Embodiment of this invention.

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

[Ion behavior detector]
FIG. 1 is a diagram showing a configuration of an ion behavior detection device according to an embodiment of the present invention, and is a diagram showing a state in which a detector is in contact with the surface of an object to be detected. FIG. 2 is a diagram showing a configuration of an ion behavior detection device according to an embodiment of the present invention, and is a diagram showing a state in which a detector is arranged near the surface of an object to be detected.

As shown in FIGS. 1 and 2, the ion behavior detection device 1 according to the present embodiment detects the behavior of the ion I in the detection object 4. The ion behavior detection device 1 includes a detection unit 2 and a control unit 3.

The detection target 4 is not particularly limited, but for example, a solid secondary battery, particularly a solid lithium secondary battery 40, is preferably used. As shown in FIGS. 1 and 2, the solid lithium secondary battery 40 includes a positive electrode layer 41, a negative electrode layer 42, a solid electrolyte layer 43, and reference electrodes 44a and 44b.

The positive electrode layer 41 is a layer having a positive electrode active material. As the positive electrode active material, a conventionally known positive electrode active material is used as the positive electrode active material of a lithium ion secondary battery or a solid lithium secondary battery. Specifically, LFP (lithium iron phosphate), ternary system (nickel / manganese / cobalt ternary system), LCO (lithium cobalt oxide) and the like are preferably used.

The negative electrode layer 42 is a layer having a negative electrode active material. As the negative electrode active material, a conventionally known negative electrode active material is used as the negative electrode active material of a lithium ion secondary battery or a solid lithium secondary battery. Specifically, Li metal, Li alloy, graphite, LTO (lithium titanate) and the like are preferably used.

The solid electrolyte layer 43 is a layer having a solid electrolyte. As the solid electrolyte, a conventionally known solid electrolyte is used as the solid electrolyte of the solid lithium secondary battery. Specific examples thereof include oxide-based solid electrolytes and sulfide-based solid electrolytes.

The reference electrodes 44a and 44b are for accurately measuring the potentials of the positive electrode layer and the negative electrode layer, respectively. For example, these reference electrodes 44a and 44b are electrically connected to a secondary battery control unit (not shown) that controls charging / discharging, temperature, etc. of the secondary battery, so that the potentials of the positive electrode layer and the negative electrode layer are increased. It is measured accurately. As a result, the secondary battery 40 can be controlled with high accuracy.

As shown in FIGS. 1 and 2, the solid lithium secondary battery 40 has a structure in which the solid electrolyte layer 43 is sandwiched between the positive electrode layer 41 and the negative electrode layer 42 arranged on both sides of the solid electrolyte layer 43, and the positive electrode layer 43 is sandwiched between the positive electrode layer 41 and the negative electrode layer 42. The structure is such that the load F is applied from both outer sides of the layer 41 and the negative electrode layer 42 (see the arrows in FIGS. 1 and 2). As a result, the contact property (contact area) between the layers is improved, and more efficient charging / discharging is possible.

The detection unit 2 detects the behavior (state) of ions in the detection object 4. More specifically, the detection unit 2 is controlled by the control unit 3 described in detail later (position control by a moving mechanism, DC power supply, AC power supply, current supply control by a pulse power supply, current value and voltage by an ammeter or a voltmeter). The value is acquired), and the behavior (state) of the ion in the detection target 4 is detected. When a solid lithium secondary battery is used as a detection target as shown in FIGS. 1 and 2, the behavior (state) of ions in the positive electrode layer 41, the negative electrode layer 42, or the solid electrolyte layer 43 constituting the electrode layer is observed. To detect.

The detector 2 has at least one detector 20 that is arranged in contact or non-contact with the object 4 to be detected. Although only one detector 20 is shown in FIGS. 1 and 2 for convenience, a plurality of detectors 20 may be provided. That is, it is not limited to the so-called single probe type, and may be a multi-probe type.

As the detector 20, for example, a cantilever as shown in FIGS. 1 and 2 is preferably used. However, the present invention is not limited to this, and for example, the shape of the tip of the lever may be rectangular instead of needle-shaped. In this case, since the planar tip surface of the rectangular detector 20 contacts or does not contact the surface of the object to be detected, it is possible to detect the behavior of ions in a wider range.

The detector 20 is configured such that at least the tip portion 20a includes a metal layer 21, an ion absorbing / releasing substance layer 22, and a solid electrolyte layer 23 in this order from the inside.

The metal layer 21 is a layer made of metal. The type of metal is not particularly limited. As the metal constituting the metal layer 21, for example, the same metal as the metal constituting the lever portion 20b of the cantilever is preferably used.

The ion absorbing / releasing substance layer 22 is a layer made of an ion absorbing / releasing substance that absorbs and releases ions. As the ion absorbing / releasing substance, the above-mentioned positive electrode active material and negative electrode active material are used, as well as H ⁺ -based redox active substances ^{such as base metals and O2-} based redox active substances. When a solid lithium secondary battery is used as the detection object 4, the ion absorption / release substance needs to be a lithium ion absorption / release substance, and the above-mentioned positive electrode active material and negative electrode active material are used.

The solid electrolyte layer 23 is a layer made of a solid electrolyte. Since only the ions pass through the solid electrolyte layer 23, it is possible to detect the ion current generated by the movement of the ions. As the solid electrolyte ^{, various solid electrolytes such as Li +} conductive electrolyte, gel + solution, dry gel, inorganic solid, oxide-based, sulfide-based, polymer, hydride, nitride, and halide can be used. .. When an H ⁺ -based oxidation-reduction active substance is used as the above-mentioned ion absorbing / releasing substance, a proton conductor is used as the solid electrolyte, and an O2 ^- based oxidation-reduction active substance is used as the above-mentioned ion absorbing / releasing substance. An oxygen ion conductor is used as the solid electrolyte.

When a solid lithium secondary battery is used as the detection target 4, a conventionally known solid electrolyte as the solid electrolyte of the above-mentioned solid lithium secondary battery is preferably used as the solid electrolyte of the solid electrolyte layer 23, and oxides are used. Systems and sulfide systems are more preferably used. In the case of an oxide-based solid electrolyte, it is possible to coat the surface of the tip portion 20a of the detector 20 by using a vapor phase method having excellent atmospheric stability. Further, in the case of a sulfide-based solid electrolyte, although there is a problem in atmospheric stability, high ionic conductivity can be obtained.

The detection unit 2 having the above configuration is controlled by the control unit 3 described in detail later (position control by a moving mechanism, DC power supply, AC power supply, current supply control by a pulse power supply, current value and voltage by an ammeter or a voltmeter). There is a correlation between the amount of ions that are transferred from the detection target 4 to the tip 20a and / or the state of the ions in the detection target 4 between the detection target 4 and the tip 20a. By detecting the value, the behavior of the ion in the detection target 4 is detected.

Here, the value that correlates with the state of ions in the detection target object 4 is, for example, an example of the electrostatic force generated between the detection target object 4 and the tip portion 20a. The detection of this electrostatic force will be described in detail in the second modification of the present embodiment.

The control unit 3 controls the detection unit 2 described above. More specifically, for example, the control unit 3 detects the position control by the moving mechanism, the current supply control by the DC power supply, the AC power supply, and the pulse power supply, and the acquisition of the current value and the voltage value by the ammeter or the voltmeter. Execute for part 2. Therefore, the control unit 3 includes a moving mechanism, a power supply, an ammeter, and a voltmeter (all not shown).

The moving mechanism moves the detector 20 described above to a position in contact with the surface of the detection object 4 or a position near the surface. The specific movement mechanism is not particularly limited, and for example, a drive source such as a piezo element or a servomotor is used.

The power supply applies direct current, alternating current, or pulse voltage to the detector 20. Since the detector 20 of the present embodiment includes an ion absorbing / releasing material layer 22 at its tip portion 20a, ions are absorbed / released from the ion absorbing / releasing material layer 22 by applying a direct current. The absorbed and released ions move between the detection target and the object 4 via the solid electrolyte layer 23 laminated on the outer side of the ion absorbing and releasing substance layer 22. That is, according to the ion behavior detection device 1 of the present embodiment, as a result of being able to continuously supply ions to the detection object 4, it is possible to accurately detect the behavior of the ions in the detection object 4. It has become.

The ammeter measures and acquires the DC current value flowing through the detector 20. The voltmeter measures and acquires the voltage value applied to the detector 20.

The ion behavior detection device 1 according to the present embodiment may further include a current collector (not shown). By bringing this current collector into contact with the detector 20 described above, the amount of ions that move from the detection target 4 to the tip 20a and / or the detection target 4 and the tip 20a It is possible to detect a value that correlates with the state of ions in the object 4 to be detected.

Further, in the present embodiment, a device capable of controlling the potential and current so that an electrochemical reaction, for example, a battery reaction occurs, for example, a potentiostat or the like may be connected to the detection object 4. For example, the structure may be such that an electrode is provided inside and the internal potential and current are measured and controlled. Further, in addition to the normal atmosphere, for example, when a sulfide system is used as the solid electrolyte layer 43, the structure is isolated so that the detection can be performed in an inert atmosphere or a vacuum state. You may. An actuator or the like capable of generating stress may be installed in the detection object 4.

The ion behavior detection device 1 according to the present embodiment having the above configuration moves from the detection object 4 to the tip portion 20a by bringing the detector 20 into contact with the surface of the detection object 4 as shown in FIG. The amount of ions (ion current) can be detected. Further, as shown in FIG. 2, by arranging the detector 20 near the surface of the detection target 4, the ions are hopping even when there is a gap between the detector 20 and the detection target 4. Since it flies through the gap (space) and moves, the amount of ions (ion current) can be detected. However, in this case, it is necessary to arrange the detector 20 at a position where ion hopping is possible.

From the above, the ionic conduction resistance can be obtained by Ohm's law based on the detected ionic current. Thereby, the behavior (state) of the ions of the detection target 4 can be detected.

Here, the ion behavior detection device 1A according to the first modification of the present embodiment will be described with reference to FIG.
FIG. 3 is a diagram showing the configuration of the ion behavior detection device 1A according to the first modification of the present embodiment. As shown in FIG. 3, the ion behavior detection device 1A according to the modification 1 is different from the above-mentioned ion behavior detection device 1 in that it includes a gas collecting unit 7.

As shown in FIG. 3, the gas collecting unit 7 is provided with a gas collecting pipe, and the generated gas is collected by the gas collecting pipe.
In the ion behavior detection device 1A according to the first modification, for example, when this device is used as a tool for measuring Li ions during the development of a solid-state battery, the gas generated as a side reaction of the electrochemical reaction is collected and the type is selected. By analyzing and identifying, the analysis result can be fed back to the development, and efficient development becomes possible.

Further, the ion behavior detection device 1B according to the second modification of the present embodiment will be described with reference to FIG.
FIG. 4 is a diagram showing the configuration of the ion behavior detection device 1B according to the second modification of the present embodiment. As shown in FIG. 4, the ion behavior detection device 1B according to the modification 2 measures the laser displacement when the lever portion 20b of the detector 20 includes the rotation shaft portion 20c with respect to the above-mentioned ion behavior detection device 1. The difference is that the device 8 is provided.

The rotation shaft portion 20c of the detector 20 of the present modification 2 is provided orthogonal to the extending direction of the lever portion 20b, and rotatably supports the tip portion 20a.

The laser displacement measuring device 8 measures the displacement of the tip portion 20a of the detector 20. For example, the laser displacement measuring device 8 has a laser emitting portion and a laser receiving portion, and the tip portion that is rotated and displaced by an electrostatic force generated between the tip portion 20a of the detector 20 and the detection object 4. The position of 20a is detected.

In this modification, the electrostatic force generated between the tip 20a and the detection object 4 corresponding to the value correlated with the state of ions in the detection object 4 between the detection object 4 and the tip 20a is applied. It can be detected, and thus the behavior of ions in the detection object 4 can be detected.

Next, measurement examples 1 to 6 of this embodiment will be described in detail with reference to the drawings.
Here, FIG. 5 is a diagram showing measurement example 1 of the ion behavior detection device according to the present embodiment. FIG. 6 is a diagram showing measurement example 2 of the ion behavior detection device according to the present embodiment. FIG. 7 is a diagram showing measurement example 3 of the ion behavior detection device according to the present embodiment. FIG. 8 is a diagram showing measurement example 4 of the ion behavior detection device according to the present embodiment. FIG. 9 is a diagram showing measurement example 5 of the ion behavior detection device according to the present embodiment. FIG. 10 is a diagram showing measurement example 6 of the ion behavior detection device according to the present embodiment. FIG. 11 is a diagram showing measurement example 6 of the ion behavior detection device according to the present embodiment. FIG. 12 is a diagram showing a measurement example 7 of the ion behavior detection device according to the present embodiment.
Although the ion behavior detection device 1 is shown as an example in FIGS. 5 to 12, the same applies to the ion behavior detection devices 1A and 1B of the modified examples.

In the measurement example 1 shown in FIG. 5, the two detectors 20 are fixedly arranged separately from each other in a state of being in contact with the surface of the positive electrode layer 41, and the current value when a direct current, an alternating current, or a pulse voltage is applied by the power supply 31. And the voltage value is measured by the ammeter 32 and the voltmeter 33. Thereby, the ionic conduction resistance inside the positive electrode layer 41 can be detected. By reversing the arrangement of the positive electrode layer 41 and the negative electrode layer 42, the ionic conduction resistance inside the negative electrode layer 42 can be detected.

In the measurement example 2 shown in FIG. 6, the two detectors 20 are separated from each other in a state of being in contact with the surface of the detection object 4 (the electrode layer of the positive electrode layer 41 or the negative electrode layer 42, the solid electrolyte layer 43, or the like). The current value and the voltage value when DC, AC, and pulse voltage are applied by the power supply 31 are measured by the current meter 32 and the voltmeter 33 while arranging and moving only one of them along the surface. Thereby, the ion conduction distribution in the detection object 4 can be detected.

In the measurement example 3 shown in FIG. 7, the two detectors 20 are inserted into the positive electrode layer 41 and fixedly arranged at a distance from each other, and the current value when a direct current, an alternating current, or a pulse voltage is applied by the power supply 31. And the voltage value is measured by the ammeter 32 and the voltmeter 33. Thereby, the ionic conduction resistance inside the positive electrode layer 41 can be detected. By reversing the arrangement of the positive electrode layer 41 and the negative electrode layer 42, the ion conduction resistance inside the negative electrode layer 42 can be detected.

In the measurement example 4 shown in FIG. 8, the two detectors 20 are separated from each other in a state of being inserted into the detection target 4 (the electrode layer of the positive electrode layer 41 and the negative electrode layer 42, the solid electrolyte layer 43, etc.). The current value and the voltage value when DC, AC, and pulse voltage are applied by the power supply 31 are measured by the current meter 32 and the voltmeter 33 while arranging them and moving only one of them along the plane direction of the detection object 4. .. Thereby, the ion conduction distribution in the detection object 4 can be detected.

In the measurement example 5 shown in FIG. 9, one detector 20 and one current collector 6 are arranged so as to be separated from each other in contact with the surface of the positive electrode layer 41 or the negative electrode layer 42, respectively, and only the detector 20 is placed on the surface. The current value and the voltage value when DC, AC, and pulse voltage are applied by the power supply 31 are measured by the current meter 32 and the voltmeter 33 while moving along the above. Thereby, the activity of the active material in the positive electrode layer 41 or the negative electrode layer 42 can be detected.

In the measurement example 6 shown in FIG. 10, one detector 20 and one current collector 6 are arranged apart from each other in contact with the active material single particles in the positive electrode layer 41 or the negative electrode layer 42, respectively, and the detectors are arranged. While moving only 20, the current value and the voltage value when DC, AC, and pulse voltage are applied by the power supply 31 are measured by the current meter 32 and the voltmeter 33. Thereby, the activity of the active material single particle in the positive electrode layer 41 or the negative electrode layer 42 can be detected.

In the measurement example 7 shown in FIG. 11, one detector 20 and one current collector 6 are arranged so as to be separated from each other in contact with the surface of the positive electrode layer 41 or the negative electrode layer 42, respectively, and only the detector 20 is placed on the surface. The voltmeter 33 measures only the voltage value when no direct current, alternating current, or pulse voltage is applied by the power supply 31 while moving along the above. Thereby, the local potential of the active material in the positive electrode layer 41 or the negative electrode layer 42 can be detected. In this case, since the detection unit 2 also has a function as a reference electrode, it is possible to detect the potential with high accuracy.

In the measurement example 8 shown in FIG. 12, one detector 20 and one current collector 6 are arranged apart from each other in a state of being in contact with the detection object, and while moving only the detector 20, direct current is supplied by the power supply 31. , AC, and the current value and the voltage value when the pulse voltage is applied are measured by the ammeter 32 and the voltmeter 33. At this time, the tip of the current collector 6 is inserted and arranged inside the detection object. As a result, the behavior (state) of the ion can be detected, and the three-dimensional structure thereof can be detected. In this case, it is preferable that the current collector 6 is covered with an insulating member other than the tip.

According to this embodiment, the following effects are achieved.

According to the present embodiment, in order to detect a value that correlates with the amount of ions moving from the detection target to the tip and / or the state of ions in the detection target between the detection target and the tip. , The behavior (state) of ions in the object to be detected can be detected with high accuracy.

For example, in a scanning probe microscope or the like, the surface state of a sample is observed by measuring the current flowing between the probe and the sample and the interatomic force. The behavior (state) of cations and anions can be detected in a non-solution environment. In addition, when measuring the electrochemical reaction, it was necessary to use an electrolytic solution in which charged particles can move, but according to this embodiment, since no electrolytic solution is used, the state is in a solid state. Can also detect the behavior (state) of ions.

Further, according to the present embodiment, if the measurement is performed while controlling the position of the detector, for example, the voltage and current distribution of a minute portion can be measured with high accuracy together with the position information. Therefore, for example, it is possible to measure the voltage and current distribution of the electrode layer (positive electrode layer, negative electrode layer) and solid electrolyte layer of a solid secondary battery and detect the state and resistance of internal ions (charged particles) with high accuracy. Therefore, by feeding back these detection results to voltage, current, temperature control, etc., the performance and durability of the solid-state secondary battery can be improved. That is, according to this embodiment, the deteriorated state of the battery, which was conventionally determined only by the voltage, can be directly detected as the deteriorated state of the electrode (active material) and the solid electrolyte, so that the solid secondary battery can be accurately detected. Deterioration suppression control is possible.

[Secondary battery device]
FIG. 13 is a diagram showing the configuration of the secondary battery device 9 according to the present embodiment. The secondary battery device 9 according to the present embodiment is characterized by including each of the above-mentioned ion behavior detection devices. The secondary battery device 9 according to the present embodiment constitutes, for example, a storage battery for a vehicle, is mounted on the vehicle, and functions on-board.

As shown in FIG. 13, the secondary battery device 9 according to the present embodiment includes a secondary battery control unit 5. The secondary battery control unit 5 controls charging, discharging, and temperature of the secondary battery. The secondary battery control unit 5 controls the charge, discharge, and temperature of the secondary battery based on the behavior of ions in the electrode layer or the solid electrolyte layer detected by the detection unit 2.

Therefore, according to the present embodiment, for example, if the measurement is performed while controlling the position of the detector, for example, the voltage and current distribution of a minute part can be measured with high accuracy together with the position information. Since the voltage and current distributions of (positive electrode layer, negative electrode layer) and solid electrolyte layer can be measured and the state and resistance of internal ions (charged particles) can be detected with high accuracy, these detection results can be used for voltage, current, and By feeding back to the temperature control or the like, the performance and durability of the solid-state secondary battery can be improved. That is, according to the present invention, the deteriorated state of the battery, which was conventionally determined only by the voltage, can be directly detected as the deteriorated state of the electrode (active material) and the solid electrolyte. Deterioration suppression control is possible.

[Scanning probe microscope]
The scanning probe microscope according to the present embodiment is characterized by including each of the above-mentioned ion behavior detection devices. Further, the detector 20 is characterized in that the tip portion 20a is a cantilever composed of a probe.

Here, the conventional scanning probe microscope (SPM) detects various physical quantities acting between the probe and the sample, such as tunnel current and atomic force, to detect the surface shape and physical properties of a minute region. Is to be measured. However, the scanning probe microscope (SPM) detects the tunnel current flowing between the probe (probe) and the sample, that is, electrons, and directly observes the generation, disappearance, movement, etc. of charged particles such as ions. It is not possible.

Further, in order to observe the electrochemical reaction occurring in the sample, an electrochemical scanning tunneling microscope capable of observing the surface while controlling the potential of the sample has been devised. However, in the electrochemical scanning tunneling microscope, in order to ensure ionic conductivity, it is necessary to bring an electrolytic solution having ionic conductivity into contact, and the object to be detected is limited to a solution system. Therefore, it cannot be applied to a solid system such as a solid secondary battery. In addition, since an electrolytic solution is used, it is impossible to measure in a reduced pressure state or a low temperature environment, and a glass capillary having high insulation properties has been used as a probe filled with an electrolytic solution for ion conduction. Therefore, laser light is used. Accurate measurement is not possible due to a large error in displacement measurement due to such factors. Furthermore, it is impossible to observe the sample in a state where stress is generated in the sample.
On the other hand, according to the scanning probe microscope according to the present embodiment, the behavior (state) of ions can be detected even in the solid state.

The present invention is not limited to the above embodiment, and modifications and improvements within the range in which the object of the present invention can be achieved are included in the present invention.

1 Ion behavior detector 2 Detector 20 Detector 20a Tip 21 Metal layer 22 Ion absorption / release material layer 23 Solid electrolyte layer 3 Control unit 31 Power supply 32 Current meter 33 Voltage meter 4 Detection target 40 Solid lithium secondary battery 41 Positive electrode Layer 42 Negative layer 43 Solid electrolyte layer 44a, 44b Reference electrode 5 Secondary battery control unit 6 Current collector 7 Gas collection unit 8 Laser displacement measuring device 9 Secondary battery device

Claims (7)

An ion behavior detection device that detects the behavior of ions in a detection target.
A detector having at least one detector arranged in contact or non-contact with the detection object,
A control unit that controls the detection unit is provided.
The detector includes, at least from the inside, a metal layer made of metal, an ion absorbing / releasing substance layer made of an ion absorbing / releasing substance that absorbs / releases ions, and a solid electrolyte layer made of a solid electrolyte. Consists of
The detection unit is controlled by the control unit, and the amount of ions moving from the detection target to the tip, and / or the ions in the detection target between the detection target and the tip. An ion behavior detection device that detects the behavior of ions in the detection target by detecting a value that correlates with the state of. The object to be detected is an electrode layer or a solid electrolyte layer of a secondary battery.
The detector has at least two detectors and is controlled by the control unit so that the tips of at least two detectors are arranged on the surface, near or inside the electrode layer or the solid electrolyte layer. The ion behavior detection device according to claim 1, wherein the ion behavior in the electrode layer or the solid electrolyte layer is detected in this state. The detection unit is controlled by the control unit, and at least one of the detectors moves along the plane direction of the electrode layer or the solid electrolyte layer to cause the behavior of ions in the electrode layer or the solid electrolyte layer. The ion behavior detection device according to claim 2, which detects the ion behavior. The object to be detected is an electrode layer or a solid electrolyte layer of a secondary battery.
The detector further includes at least one current collector, and is controlled by the control unit so that the tip of at least one detector is arranged on the surface, near or inside the electrode layer or the solid electrolyte layer. The ion behavior detection device according to claim 1, wherein the ion behavior is detected in the electrode layer or the solid electrolyte layer in a state where at least one of the current collectors is in contact with the electrode layer or the solid electrolyte layer. .. The detection unit is controlled by the control unit so that at least one tip of the detector is arranged on or near the surface of the electrode layer or the solid electrolyte layer, and at least one of the current collectors is said. The ion behavior detection device according to claim 4, wherein the ion behavior is detected in the electrode layer or the solid electrolyte layer while being inserted inside the electrode layer or the solid electrolyte layer. The ion behavior detection device according to any one of claims 1 to 5.
It is equipped with a secondary battery control unit that controls charging, discharging, and temperature of the secondary battery.
The object to be detected is an electrode layer or a solid electrolyte layer of a secondary battery.
The secondary battery control unit is a secondary battery device that controls charging, discharging, and temperature of the secondary battery based on the behavior of ions in the electrode layer or the solid electrolyte layer detected by the detection unit. The ion behavior detection device according to any one of claims 1 to 5 is provided.
The detector is a scanning probe microscope in which the tip is a cantilever composed of a probe.

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