JP5880475B2 - Functional oxide, method for producing functional oxide, electrochemical device, sensor and equipment - Google Patents

Description

  The present disclosure relates to a functional oxide, a method for producing the functional oxide, an electrochemical device, a sensor, and an apparatus. More specifically, the present disclosure includes, for example, functional oxides suitable for use in solid electrolytes of various electrochemical devices, methods for producing the same, various electrochemical devices using the functional oxides as solid electrolytes, The present invention relates to a sensor for detecting an oxidizing gas or temperature and various devices using the sensor.

  FePt nanoparticles are useful as magnetic materials (see, for example, Patent Documents 1 and 2). Conventionally, FePt nanoparticles are typically synthesized by a wet method and obtained in a form dispersed in a liquid using a surfactant (see, for example, Patent Documents 3 and 4).

JP 2006-66036 A JP 2012-243379 A JP 2008-57037 A JP 2009-97038 A

J. Matos et al., Applied Catalysis A: General 152 (1997) 27-42

  However, when manufacturing a device using FePt nanoparticles, it is necessary to collect and use FePt nanoparticles present in a dispersed form in a liquid. The method of use has been limited, such as using aggregates of FePt nanoparticles.

  Thus, the problem to be solved by the present disclosure is that a functional oxide that can be used as various functional materials such as superionic conductors and catalysts, and that is easy to manufacture and handle, and the functional oxide can be easily used. It is providing the manufacturing method of the functional oxide which can be manufactured in this.

  Another problem to be solved by the present disclosure is to provide a high-performance electrochemical device using the above-described excellent functional oxide as a solid electrolyte.

  Still another problem to be solved by the present disclosure is to provide a sensor using the excellent functional oxide as described above and a device using the sensor.

  The above and other problems will become apparent from the following description of the present specification with reference to the accompanying drawings.

In order to solve the above problems, the present disclosure provides:
A metal oxide having a perovskite crystal structure;
It is a functional oxide containing FePt nanoparticles dispersed in the metal oxide.

The metal oxide is preferably one that is stable in a reducing atmosphere and can dissolve Fe and Pt in an oxidizing atmosphere. Specifically, this metal oxide is, for example, A (M, Fe) O _3-y (where A = Ca, Sr, Ba; M = Ti, Zr; 0 ≦ y <3) or Ln (M , Fe) O _3-y (where Ln = La, Ce, Pr, Nd, Sm; M = Al, Ga, Sc; 0 ≦ y <3). Here, y is an oxygen deficiency and is not particularly limited as long as the metal oxide can maintain a perovskite crystal structure, but is generally small, for example, 0.5 or less. The functional oxide can be used as, for example, an oxygen filter material in addition to a superionic conductor and a catalyst.

In a typical example, metal _{oxide, SrTi 1-x Fe x O} 3-y; a (0.09 ≦ x ≦ 0.11 0 ≦ y <3).

In addition, this disclosure
By performing a reduction treatment by heating a mixture containing a metal oxide having a perovskite-type crystal structure and containing at least two kinds of metals different from Fe and Pt and a raw material of Fe and Pt in a reducing atmosphere. This is a method for producing a functional oxide for depositing FePt nanoparticles.

Here, typically, for example, the reduction treatment is performed by heating the metal oxide to a temperature of 600 ° C. or higher and 1000 ° C. or lower in a reducing atmosphere. Examples of the reducing atmosphere include hydrogen (H ₂ ), carbon monoxide (CO), hydrogen sulfide (H ₂ S), sulfur dioxide (SO ₂ ), and the like. At least two kinds of metals different from Fe and Pt are, for example, at least one kind of metal selected from the group consisting of Ca, Sr, Ba, La, Ce, Pr, Nd and Sm, and Ti, Zr, Al, and Ga. And at least one metal selected from the group consisting of Sc.

In addition, this disclosure
Having a solid electrolyte,
The solid electrolyte is
A metal oxide having a perovskite crystal structure;
An electrochemical device comprising a functional oxide comprising FePt nanoparticles dispersed in the metal oxide.

  The electrochemical device may be basically any device, and specifically, for example, various batteries using lithium (Li) or the like, capacitors, sensors, Li ion filters, and the like. The battery is a primary battery, a secondary battery, an air battery, a fuel cell, or the like. The secondary battery is, for example, a lithium ion battery, and an all solid lithium ion battery can be realized by using a solid electrolyte.

In addition, this disclosure
A metal oxide having a perovskite crystal structure;
The sensor includes a functional oxide including FePt nanoparticles dispersed in the metal oxide.

This sensor is typically held at a temperature below the maximum temperature at which the FePt nanoparticles are dissolved (hereinafter referred to as critical temperature if necessary) when the functional oxide is exposed to an oxidizing atmosphere. It is used in a state where the functional oxide is exposed to an oxidizing atmosphere. Examples of the oxidizing atmosphere include air, oxygen (O ₂ ), ozone (O ₃ ), carbon dioxide (CO ₂ ), and the like. This sensor can use a phenomenon in which the functional oxide loses magnetism when the FePt nanoparticles are dissolved. That is, when this sensor is kept at a temperature below the critical temperature, when the functional oxide is exposed to an oxidizing atmosphere, the FePt nanoparticles having magnetic properties dissolve and disappear, so that the functional oxide becomes magnetic. Therefore, it is possible to detect that the functional oxide has been exposed to the oxidizing atmosphere by detecting it electrically or magnetically. Alternatively, when the functional oxide of this sensor is exposed to an oxidizing atmosphere, the functional oxide becomes magnetic at a temperature lower than the critical temperature because the magnetic FePt nanoparticles dissolve and disappear. Therefore, by detecting this electrically or magnetically, it is possible to detect that the temperature is lower than the critical temperature.

In addition, this disclosure
Having at least one sensor,
The sensor
A metal oxide having a perovskite crystal structure;
The device includes a functional oxide including FePt nanoparticles dispersed in the metal oxide.

  This device may be basically any device as long as it performs some kind of operation control (switching or the like) using the output of the sensor. As an example of this equipment, various processing devices that perform necessary processing at a temperature lower than the critical temperature, and if the intrusion of an oxidizing gas into the processing chamber causes a failure in the target processing, the processing chamber It is a safety device installed inside. That is, in this safety device, if the sensor is held at a temperature lower than the critical temperature, the processing chamber leaks for some reason, or several gas introduction pipes are provided to introduce several kinds of gases into the processing chamber. If the functional oxide is exposed to an oxidizing gas, that is, an oxidizing atmosphere as a result of a gas switching accident, the FePt nanoparticles dissolve and disappear, thereby causing the functional oxide to disappear. Therefore, it is possible to detect that the oxidizing gas has entered the inside of the processing chamber by detecting this electrically or magnetically. Then, using the output of the sensor at this time, the processing can be stopped, or the supply of gas to the processing chamber can be stopped. By doing so, the processing apparatus can be operated safely.

  In the present disclosure described above, the functional oxide is easy to handle because FePt nanoparticles are dispersed in the metal oxide. In addition, this functional oxide has a perovskite type crystal structure, and a simple starting material is a mixture containing a metal oxide containing at least two kinds of metals different from Fe and Pt and a raw material of Fe and Pt. It can be easily manufactured through a simple process.

  According to the present disclosure, it is possible to obtain a functional oxide that can be used as various functional materials such as a superionic conductor and a catalyst, and that is easy to manufacture and handle. And various high performance electrochemical devices, such as an all-solid-state lithium ion battery, can be implement | achieved using such an outstanding functional oxide for a solid electrolyte. Alternatively, a sensor based on a novel principle capable of detecting an oxidizing atmosphere or temperature can be realized. Furthermore, various devices based on a novel principle can be realized using this sensor.

It is sectional drawing which shows typically the functional oxide by 1st Embodiment. It is a basic diagram which shows the X-ray-diffraction pattern of the sample after hold | maintaining at 600 degreeC for 20 hours in an Example. Is a schematic diagram showing an X-ray diffraction pattern of _{SrTi 0.9 Fe 0.1 O 3-y} -2vol% Pt after after the reduction treatment and reoxidation process in the Examples. FIG. 5 is a drawing-substituting photograph showing a transmission electron microscope image after reduction treatment at 600 ° C. in an H ₂ -1.9% H ₂ O atmosphere in Examples. It is sectional drawing which shows a mode that the space charge layer is formed around the FePt nanoparticle in the functional oxide by 1st Embodiment. It is a basic diagram which shows the result of having performed the magnetization measurement before precipitation of FePt nanoparticle in the functional oxide by 1st Embodiment. It is a basic diagram which shows the result of having performed the magnetization measurement after precipitation of the FePt nanoparticle in the functional oxide by 1st Embodiment. It is a basic diagram which shows typically the all-solid-state lithium ion battery by 2nd Embodiment. It is sectional drawing which shows typically the gas / temperature sensor by 3rd Embodiment. It is sectional drawing which shows typically the processing apparatus by 4th Embodiment.

Hereinafter, modes for carrying out the invention (hereinafter referred to as “embodiments”) will be described. The description will be given in the following order.
1. 1st Embodiment (functional oxide and its manufacturing method)
2. Second embodiment (all-solid-state lithium ion battery)
3. Third embodiment (gas / temperature sensor)
4). Fourth embodiment (processing apparatus)

<1. First Embodiment>
[Functional oxides]
As shown in FIG. 1, the functional oxide 10 includes a metal oxide 11 having a perovskite crystal structure as a parent phase, and FePt nanoparticles 12 dispersed in the metal oxide 11.

  The size of the FePt nanoparticles 12 is generally 0.5 nm to 100 nm, typically 1 nm to 20 nm, but is not limited thereto.

Examples of the metal oxide 11 include A (M, Fe) O _3-y which is a 2-4 type perovskite oxide (where A = Ca, Sr, Ba; M = Ti, Zr; 0 ≦ y <3). ) Or Ln (M, Fe) O _3-y which is a 3-3 type perovskite oxide (where Ln = La, Ce, Pr, Nd, Sm; M = Al, Ga, Sc; 0 ≦ y <3) From these, it is appropriately selected according to the function to be given to the functional oxide.

  The volume fraction of the FePt nanoparticles 12 in the functional oxide 10 is not particularly limited and is selected as necessary. For example, the volume fraction of the metal oxide 11 is 1 vol% or more and 10 vol% or less, typically It is 1 vol% or more and 3 vol% or less. Alternatively, the molar ratio of FePt nanoparticles 12 in the functional oxide 10 is, for example, 0.04 mol or more and 0.4 mol or less, typically 0.04 mol or more and 0 or less with respect to 1 mol (mol) of the metal oxide 11. .12 mol or less.

[Method for Producing Functional Oxide 10]
A method for producing the functional oxide 10 will be described.
First, for example, a raw material of Fe, a raw material of Pt, and at least two kinds of metal raw materials different from Fe and Pt constituting the metal oxide 11 are weighed to prepare a solution dissolved in a solvent.

  Next, this solution is heated to a temperature of, for example, 300 ° C. or more and 500 ° C. or less, and then cooled to room temperature, for example, to obtain a solid.

  Next, the solid thus obtained is maintained at a temperature of, for example, 550 ° C. or more and 650 ° C. or less, for example, for 1 hour or more and 30 hours or less to obtain a powder.

  Next, the powder is subjected to a hydrogen atmosphere (no humidification or a small amount of water vapor. The small amount of water vapor is usually about the amount of water vapor in the air, or the amount of water vapor contained in the gas bubbling water). For example, the reduction treatment is performed by holding at a temperature of 550 ° C. to 1100 ° C. for 10 minutes to 3 hours. By this reduction treatment, FePt nanoparticles are precipitated in the powder. Thereafter, heat treatment (sintering) is performed, for example, in the atmosphere at a temperature of 900 ° C. or higher and 1100 ° C. or lower for the purpose of increasing the density of the pellets, if necessary.

  As described above, as shown in FIG. 1, the functional oxide 10 in which the FePt nanoparticles 12 are dispersed in the metal oxide 11 can be obtained.

<Example>
・ Process 1
The reagent shown in Table 1 was put into a beaker, and the reagent was stirred on a hot stirrer heated to 100 ° C. or lower to obtain a yellow solution.

・ Process 2
The solution obtained in step 1 was heated to 400 ° C. with a hot stirrer to obtain a brown solid.

・ Process 3
The solid obtained in step 2 was placed in a muffle furnace and held at 600 ° C. for a total of 20 hours. As shown in FIG. 2, the powder thus obtained was confirmed to be a perovskite single phase by X-ray diffraction.

・ Process 4
The powder obtained in Step 3 was subjected to a reduction treatment by holding it at 600 ° C. or 1000 ° C. for 1 hour under a hydrogen atmosphere (no humidification or 1.9% water vapor). Separately, heat treatment was performed for 1 hour at 1000 ° C. in the atmosphere. As shown in FIG. 3, X-ray diffraction suggested that FePt nanoparticles were generated in the sample after the reduction treatment. In addition, Pt nanoparticles were generated instead of FePt nanoparticles when kept at 1000 ° C. in the atmosphere.

  As shown in FIG. 4, FePt nanoparticles having a size of about 1 nm to 20 nm in the reduction treatment at 600 ° C. (for example, in FIG. 4) by transmission electron microscope observation / energy dispersive X-ray spectroscopy (TEM / EDX). It was confirmed that two circular FePt nanoparticles were observed in the upper left part).

  When the sample on which the FePt nanoparticles were deposited was held again at 600 ° C. in the atmosphere, it was suggested by X-ray diffraction that the FePt nanoparticles were re-dissolved in the perovskite (see FIGS. 3B and C). On the other hand, Pt nanoparticles generated at 1000 ° C. in the atmosphere did not re-dissolve (see FIG. 3A).

Here, in particular metal oxide 11 _{SrTi 1-x Fe x O 3} -y; the case is (x = 0.1 0 ≦ y < 3), will be described together features of functional oxide 10 following (1) to (4).

(1) In this functional oxide _{10, SrTi 1-x Fe x O} 3-y FePt nanoparticles was produced in the metal oxide 11 of 12 has a particle size of 1nm or more 20nm or less and very small is there. The produced FePt nanoparticles 12 are stable not only in hydrogen but also in an oxidizing atmosphere at room temperature.

(2) Moreover, the produced FePt nanoparticles 12 have a property of being stable up to a high temperature in a reducing atmosphere. Specifically, the generated FePt nanoparticles 12 do not grow in a reducing atmosphere at a high temperature (for example, up to about 1000 ° C.) and exist stably as fine nanoparticles. On the other hand, in an oxidizing atmosphere at a temperature higher than 600 ° C., coarse grains of Pt (not FePt) are precipitated. Therefore, it can be said that the Pt nanoparticles react with Fe in the matrix oxide and are alloyed to become FePt nanoparticles 12 so that they do not grow to a high temperature and exist stably as fine particles.

(3) At a temperature of 600 ° C. or lower, the FePt nanoparticles 12 are taken into the parent phase oxide and disappear in an oxidizing atmosphere. That is, the precipitation (reducing atmosphere) and re-solution (oxidizing atmosphere) of the FePt nanoparticles 12 occur reversibly.

(4) This functional oxide 10 is stable in hydrogen. That is, SrTiO ₃ is stable even when exposed to hydrogen. SrTi _1-z Fe _z O _{3-y in} which a part of Ti is substituted with Fe is also stable in hydrogen unless the amount of Fe is too large. Therefore, the functional oxide 10 or the FePt nanoparticles 12 dispersed therein are stable even in a reducing atmosphere.

  Next, a typical application example of the functional oxide 10 according to the first embodiment will be described.

(1) Superionic Conductive Material The functional oxide 10 in which the FePt nanoparticles 12 are dispersed in the metal oxide 11 bulk increases the ionic conduction (enhancement) at the heterointerface between the metal oxide 11 and the FePt nanoparticles 12. It becomes a superionic conductive material reflecting the characteristics of That is, as shown in FIG. 5, at the heterointerface between the metal oxide 11 and the FePt nanoparticle 12, charge movement occurs due to the difference in work function between them, and the space charge layer 13 is formed, resulting in band bending. As a result, an increase in ionic conduction occurs. This superionic conductive material is suitable, for example, as a solid electrolyte for various electrochemical devices.

(2) Catalyst The FePt nanoparticles 12 serve as catalysts for various chemical reactions, and thus the functional oxide 10 can be used as a catalyst as a whole. In particular, when used as a redox catalyst, durability at high temperatures (usually metal coarsens at high temperatures) is an important factor, but this functional oxide 10 has high durability at high temperatures. Is as already described. Further, in this functional oxide 10, the FePt nanoparticles 12 are formed by exposing the functional oxide 10 to an oxidizing atmosphere at a temperature of, for example, 600 ° C. or lower after the function of the catalyst is lowered after being used as a catalyst for a certain time. The FePt nanoparticles 12 can be deposited again by exposing the functional oxide 10 to a reducing atmosphere at a temperature of, for example, 600 to 1000 ° C. by dissolving the metal oxide 11 in a solid solution. By doing so, the FePt nanoparticles 12 and thus the functional oxide 10 can be refreshed and the catalytic activity can be recovered.

(3) Oxygen filter The functional oxide 10 can be used as an oxygen filter, particularly a room temperature oxygen filter.

(4) Magnetic body Since the FePt nanoparticles 12 are a magnetic material, the functional oxide 10 in which the FePt nanoparticles 12 are dispersed in the metal oxide 11 can also be used as a magnetic material as a whole. The functional oxide 10 can lose the magnetism because the FePt nanoparticles 12 can be eliminated by exposing the functional oxide 10 to an oxidizing atmosphere at a temperature of 600 ° C. or less, for example. That is, the functional oxide 10 can be reversibly converted between a magnetic material and a nonmagnetic material by adjusting the atmosphere.

  6 and 7 show the results of measuring the magnetization of the functional oxide 10 before and after the precipitation of the FePt nanoparticles 12. The functional oxide 10 is produced according to the example. As shown in FIG. 6, before the precipitation of the FePt nanoparticles 12, the magnetization value is almost zero, that is, there is no magnetism, regardless of the external magnetic field. On the other hand, as shown in FIG. 7, after the precipitation of FePt nanoparticles 12, a magnetization (M) -magnetic field (H) curve whose magnetization depends on an external magnetic field was obtained, and magnetism was obtained. The saturation magnetization is about 0.5 emu / cc.

  As described above, according to the first embodiment, the following advantages can be obtained. That is, the functional oxide 10 in which the FePt nanoparticles 12 are dispersed in the metal oxide 11 having a perovskite crystal structure is easy to handle and has a wide range of applications to various devices. Further, the FePt nanoparticles 12 dispersed in the metal oxide 11 can be freely re-dissolved and precipitated again by adjusting the atmosphere. The functional oxide 10 can be used as various functional materials such as a superionic conductor, a catalyst, an oxygen filter, and a magnetic material that can be easily converted into a nonmagnetic material.

  In addition, for example, the excellent functional oxide 10 is applied as a solid electrolyte of, for example, an all-solid-state lithium ion battery, thereby exhibiting charge / discharge characteristics comparable to those of a conventional lithium-ion battery, and extremely safe. Can be realized.

<2. Second Embodiment>
[All-solid-state lithium-ion battery]
Next, a second embodiment will be described. In the second embodiment, the functional oxide 10 according to the first embodiment is used as the solid electrolyte layer.

  FIG. 8 schematically shows the basic configuration of this all solid-state lithium ion battery.

As shown in FIG. 8, this all solid lithium ion battery has a structure in which a positive electrode 20 and a negative electrode 30 are opposed to each other with a functional oxide 10 constituting a solid electrolyte. Examples of the positive electrode 20 include lithium cobaltate (LCO) -based materials (typically LiCoO ₂ ), lithium nickelate (LNO) -based materials, nickel-cobalt-manganese (NCM) -based materials, and lithium manganate (LMO) -based materials. Materials, olivine-based materials, sulfur (S) -based materials and the like are used, but are not limited thereto. Examples of the negative electrode 30 include, but are not limited to, a material containing graphite, silicon (Si), tin (Sn), zinc (Zn), lithium titanate (LTO), or the like.

[Operation of all-solid-state lithium-ion battery]
In this all-solid-state lithium ion battery, during charging, lithium ions (Li ⁺ ) move from the positive electrode 20 through the functional oxide 10 constituting the solid electrolyte to the negative electrode 30 to convert electrical energy into chemical energy. To store electricity. At the time of discharging, lithium ions return from the negative electrode 30 through the functional oxide 10 to the positive electrode 20 to generate electric energy.

  According to the second embodiment, a novel all-solid lithium ion battery using a solid electrolyte made of the functional oxide 10 as the electrolyte layer can be realized. This all-solid-state lithium ion battery exhibits the same charge / discharge characteristics as a conventional lithium ion battery, and can obtain extremely high safety.

This all-solid-state lithium ion battery is, for example, a notebook personal computer, a PDA (personal digital assistant), a mobile phone, a cordless phone, a video movie, a digital still camera, an electronic book, an electronic dictionary, a portable music player, a radio, a headphone , Game machine, navigation system, memory card, heart pacemaker, hearing aid, electric tool, electric shaver, refrigerator, air conditioner, TV, stereo, water heater, microwave oven, dishwasher, washing machine, dryer, lighting equipment, toy, Driving power or auxiliary power for medical devices, robots, road conditioners, traffic lights, railway cars, golf carts, electric carts, electric cars (including hybrid cars), power for buildings or power generation facilities such as houses Installed in storage power supply, etc. It can be used to power these. In an electric vehicle, a conversion device that converts electric power into driving force by supplying electric power is generally a motor. Examples of the control device that performs information processing related to vehicle control include a control device that displays the remaining battery level based on information related to the remaining battery level. This lithium ion battery can also be used as a power storage device in a so-called smart grid. Such a power storage device can not only supply power but also store power by receiving power from another power source. As other power sources, for example, thermal power generation, nuclear power generation, hydroelectric power generation, solar cells, wind power generation, geothermal power generation, fuel cells (including biofuel cells) and the like can be used.

<3. Third Embodiment>
[Gas / temperature sensor]
Next, a third embodiment will be described. In the third embodiment, the functional oxide 10 according to the first embodiment is used as a sensor material.

  FIG. 9 schematically shows the basic configuration of this gas / temperature sensor.

  As shown in FIG. 9, in this gas / temperature sensor, a functional oxide 10 as a sensor material is provided on a support 40 having a magnetic sensor (not shown). As the magnetic sensor, various conventionally known ones can be used, for example, a Hall element. This magnetic sensor is for measuring the magnetic field in the vicinity of the functional oxide 10, and when the FePt nanoparticles 12 in the functional oxide 10 have magnetism, the magnetic field is measured and the FePt nanoparticles 12 disappear. Sometimes the magnetic field is not measured.

[Operation of gas / temperature sensor]
For example, the functional oxide 10 is held at a temperature not higher than a critical temperature (for example, 600 ° C.). In this state, the atmosphere surrounding the functional oxide 10 is not an oxidizing atmosphere. At this time, since the FePt nanoparticles 12 present in the functional oxide 10 have magnetism, the magnetic field is detected by the magnetic sensor. When the functional oxide 10 is exposed to an oxidizing atmosphere for some reason, the FePt nanoparticles 12 in the functional oxide 10 disappear, so that the magnetic field detected by the magnetic sensor decreases or the magnetic field is detected. Disappear. For this reason, it is possible to detect that the functional oxide 10 has been exposed to an oxidizing atmosphere by detecting the magnetic field in the vicinity of the functional oxide 10 with a magnetic sensor. In other words, an oxidizing atmosphere can be detected.

  According to the third embodiment, a gas / temperature sensor based on a novel principle can be realized.

<4. Fourth Embodiment>
[Processing equipment]
Next, a fourth embodiment will be described. In the fourth embodiment, a processing apparatus will be described.

  FIG. 10 shows the processing chamber 50 of this processing apparatus. This processing apparatus is for performing various types of processing in which a failure occurs when an oxidizing gas enters the processing chamber 50. At least one gas pipe 51 for introducing various non-oxidizing gases into the processing chamber 50 is attached to the wall of the processing chamber 50. A gas / temperature sensor 52 is attached to the inner wall of the processing chamber 50 by a fixture (not shown). As the gas / temperature sensor 52, the gas / temperature sensor according to the third embodiment is used. The output of the gas / temperature sensor 52 is sent to the control circuit of the processing apparatus so that the operation of the processing apparatus can be controlled. Although not shown, an evacuation system is connected to the processing chamber 50 so that the inside of the processing chamber 50 can be evacuated.

[Usage of processing equipment]
A method of using this processing apparatus will be described.
First, it is assumed that the gas / temperature sensor 52 is maintained at a temperature equal to or lower than a critical temperature (for example, 600 ° C.). It is assumed that the processing chamber 50 leaks for some reason or a gas switching accident occurs when several systems of gas introduction pipes for introducing several kinds of gases are provided in the processing chamber 50. As a result, when the functional oxide 10 is exposed to an oxidizing gas, that is, an oxidizing atmosphere, the FePt nanoparticles 12 lose their magnetism due to the solid solution and disappearance. By detecting the target or magnetically, it is possible to detect that the oxidizing gas has entered the processing chamber 50. Then, using the output of the gas / temperature sensor 52 at this time, the operation of the processing apparatus may be stopped to stop the processing, or the supply of gas from the gas pipe 51 to the processing chamber 50 may be stopped. it can. By doing so, the processing apparatus can be operated safely. That is, the gas / temperature sensor 52 can be used as a safety device.

  According to the fourth embodiment, since the gas / temperature sensor 52 is attached inside the processing chamber 50, the processing apparatus can be operated safely.

  Although the embodiments and examples of the present disclosure have been specifically described above, the present disclosure is not limited to the above-described embodiments and examples, and various modifications can be made.

  For example, the numerical values, structures, configurations, shapes, materials, and the like given in the above-described embodiments and examples are merely examples, and different numerical values, structures, configurations, shapes, materials, etc. are used as necessary. Also good.

  In addition to the FePt nanoparticles 12, the nanoparticles dispersed in the metal oxide 11 include nanoparticles made of other alloys or simple metals, and nanoparticles made of a metal oxide different from the metal oxide 11. Is also possible. For example, nanoparticles made of a Ni—Mo alloy, a Co—Mo alloy, a Ni—W alloy, a Pd—Pb alloy, a Cu—Zn alloy, or the like may be used. Here, the Ni—Mo alloy can be used as a hydrogenation catalyst for ethylene at 300 ° C. (see Non-Patent Document 1). In addition, a Co—Mo alloy, a Ni—Mo alloy, and a Ni—W alloy can be used as a hydrodesulfurization catalyst. Pd—Pb alloys and Cu—Zn alloys can be used as hydrogenation catalysts.

In addition, this technique can also take the following structures.
(1) A functional oxide comprising a metal oxide having a perovskite crystal structure and FePt nanoparticles dispersed in the metal oxide.
(2) The functional oxide according to (1), wherein the metal oxide is stable in a reducing atmosphere and can dissolve Fe and Pt in an oxidizing atmosphere.
(3) The metal oxide is A (M, Fe) O _3-y (where A = Ca, Sr, Ba; M = Ti, Zr; 0 ≦ y <3) or Ln (M, Fe) O ₃ The functional oxide according to (1) or (2), wherein _-y (where Ln = La, Ce, Pr, Nd, Sm; M = Al, Ga, Sc; 0 ≦ y <3).
(4) The functional oxide according to any one of (1) to (3), wherein the functional oxide is a superionic conductor or a catalyst.
(5) The metal oxide _{SrTi 1-x Fe x O 3} -y; according to any one (0.09 ≦ x ≦ 0.11 0 ≦ y <3) consisting of (1) to (4) Functional oxide.
(6) A reduction treatment is performed by heating a mixture containing a metal oxide having a perovskite crystal structure and containing at least two kinds of metals different from Fe and Pt, and a raw material of Fe and Pt in a reducing atmosphere. A method for producing a functional oxide that precipitates FePt nanoparticles by performing.
(7) The method for producing a functional oxide according to (6), wherein the reduction treatment is performed by heating the metal oxide to a temperature of 600 ° C. or higher and 1000 ° C. or lower in a reducing atmosphere.
(8) At least two kinds of metals different from Fe and Pt are at least one kind of metal selected from the group consisting of Ca, Sr, Ba, La, Ce, Pr, Nd and Sm, and Ti, Zr, and Al. The method for producing a functional oxide according to (6) or (7), comprising at least one metal selected from the group consisting of Ga, and Sc.
(9) An electrochemical device including a solid electrolyte, wherein the solid electrolyte includes a functional oxide including a metal oxide having a perovskite crystal structure and FePt nanoparticles dispersed in the metal oxide.
(10) The electrochemical device according to (9), wherein the electrochemical device is a battery, a capacitor, a sensor, or a lithium ion filter.
(11) The electrochemical device according to (10), wherein the battery is a primary battery, a secondary battery, an air battery, or a fuel cell.
(12) A sensor including a functional oxide including a metal oxide having a perovskite crystal structure and FePt nanoparticles dispersed in the metal oxide.
(13) When the functional oxide is exposed to an oxidizing atmosphere, the FePt nanoparticles are used at a temperature below the maximum temperature at which they dissolve, or the functional oxide is exposed to an oxidizing atmosphere. The sensor according to the above (12), which is used in a state where
(14) The sensor according to (12) or (13), wherein the functional oxide loses magnetism when the FePt nanoparticles are dissolved.

  DESCRIPTION OF SYMBOLS 10 ... Functional oxide, 11 ... Metal oxide, 12 ... FePt nanoparticle, 13 ... Space charge layer, 20 ... Positive electrode, 30 ... Negative electrode, 40 ... Support body, 50 ... Processing chamber, 51 ... Gas piping, 52 ... Gas / temperature sensor

Claims (13)

A metal oxide having a perovskite crystal structure;
The FePt nanoparticles dispersed in the metal oxide and Nde including,
The metal oxide is stable in a reducing atmosphere and can dissolve Fe and Pt in an oxidizing atmosphere. A (M, Fe) O _3-y (where A = Ca, Sr, Ba; M = Ti, Zr; 0 ≦ y <3) or Ln (M, Fe) O _3-y (where Ln = La, Ce, Pr, Nd, Sm; M = Al, Ga, Sc; 0 ≦ y < 3)
Functional oxide. The functional oxide is a superionic conductor or catalyst .
The functional oxide according to claim 1 . The metal oxide is _{SrTi 1-x Fe x O 3} -y; consisting (0.09 ≦ x ≦ 0.11 0 ≦ y <3),
The functional oxide according to claim 1 or claim 2 .   By performing a reduction treatment by heating a mixture containing a metal oxide having a perovskite-type crystal structure and containing at least two kinds of metals different from Fe and Pt and a raw material of Fe and Pt in a reducing atmosphere. The manufacturing method of the functional oxide which deposits FePt nanoparticle. The metal oxide is heated to a temperature of 600 ° C. or higher and 1000 ° C. or lower in a reducing atmosphere to perform a reduction treatment .
The manufacturing method of the functional oxide of Claim 4 . The at least two kinds of metals different from Fe and Pt are at least one kind of metal selected from the group consisting of Ca, Sr, Ba, La, Ce, Pr, Nd and Sm, and Ti, Zr, Al, Ga and Including at least one metal selected from the group consisting of Sc ,
The manufacturing method of the functional oxide of Claim 4 or Claim 5 . Having a solid electrolyte,
The solid electrolyte is
A metal oxide having a perovskite crystal structure;
An electrochemical device comprising a functional oxide comprising FePt nanoparticles dispersed in the metal oxide. The electrochemical device is a battery, a capacitor, a sensor or a lithium ion filter .
The electrochemical device according to claim 7 . The battery is a primary battery, a secondary battery, an air battery or a fuel cell .
The electrochemical device according to claim 8 . A metal oxide having a perovskite crystal structure;
A functional oxide containing FePt nanoparticles dispersed in the metal oxide ,
Sensor. When the functional oxide is exposed to an oxidizing atmosphere, the FePt nanoparticles are used while being held at a temperature below the maximum temperature at which they dissolve, or the functional oxide is exposed to an oxidizing atmosphere. Used ,
The sensor according to claim 10 . Using the phenomenon that the functional oxide loses magnetism when the FePt nanoparticles are dissolved .
The sensor according to claim 10 or 11 . Having at least one sensor,
The sensor
A metal oxide having a perovskite crystal structure;
A device comprising a functional oxide comprising FePt nanoparticles dispersed in the metal oxide.