CN112098471A - Gas sensor - Google Patents
Gas sensor Download PDFInfo
- Publication number
- CN112098471A CN112098471A CN202010552699.8A CN202010552699A CN112098471A CN 112098471 A CN112098471 A CN 112098471A CN 202010552699 A CN202010552699 A CN 202010552699A CN 112098471 A CN112098471 A CN 112098471A
- Authority
- CN
- China
- Prior art keywords
- gas
- fluoride
- hydroxide
- detection
- adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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Images
Classifications
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
- G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
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- Chemical & Material Sciences (AREA)
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Abstract
Provided is a gas sensor which, even in an environment in which a gas to be measured contains a fluoride-based gas that is a corrosive gas, can maintain detection performance without being corroded by the fluoride-based gas, can detect the gas to be detected with high accuracy and stability over a long period of time, and has excellent durability. A gas sensor (1) for detecting a specific detection target gas in a gas to be measured is provided with: a detection unit (10) that includes a detection element for detecting a gas to be detected, and an adsorption conversion unit (20) for adsorbing a fluoride-based gas contained in a gas to be measured on the upstream side of the detection unit (10) in a gas flow path through which the gas to be measured flows down the detection unit (10); the adsorption conversion section (20) is selected from a hydroxide-based adsorption conversion material (21) in which an alkali hydroxide is supported on an insoluble carrier, and an ion exchange-based adsorption conversion material (22) in which a strongly basic anion exchange group is supported on an insoluble carrier.
Description
Technical Field
The present invention relates to a gas sensor, and more particularly to a gas sensor that can be applied to detection of a detection target gas in an environment in which a measurement target gas contains a fluoride-based gas that is a corrosive gas, and that can stably maintain detection performance for a long period of time.
Background
Gas sensors are used for safety applications such as detection of combustible gases and toxic gases, vehicle-mounted applications such as control and maintenance of lithium ion batteries (hereinafter sometimes referred to as "LIBs") mounted in hybrid vehicles and electric vehicles and fuel cells mounted in fuel cell vehicles, industrial applications such as combustion control and chemical reaction monitoring in industrial production processes, environmental applications such as atmospheric monitoring, and the like, and have various application ranges and use environments including various situations. Therefore, a highly corrosive gas may be contained in the gas to be measured, and if the gas to be measured is exposed to such a corrosive gas for a long time, the detection element of the gas sensor deteriorates, and the detection performance deteriorates.
For example, a lithium ion battery used for a power source, a power storage system, and the like of a hybrid vehicle, an electric vehicle, a mobile phone, a notebook computer, a digital camera, and the like is typically composed of a positive electrode having a lithium material such as lithium oxide as a constituent material, a negative electrode having a carbon material as a constituent material, and an electrolyte solution. The electrolyte solution is composed of an electrolyte salt and an organic solvent, and a combination of various compounds corresponding to the electrode material is used. For example, lithium hexafluorophosphate (LiPF) is mentioned6) Lithium borofluoride (LiBF)4) And mixtures of fluoride-based salts and carbonate-based organic solvents. The organic solvent is a flammable gas that may cause ignition or explosion, and is a main component of gas generated by LIB, for example, when LIB fails, and therefore the organic solvent-based gas is a detection target in the gas sensor. Therefore, by detecting the organic solvent-based gas, it is possible to detect a failure of LIB and a sign of the failure, prevent the failure, and contribute to appropriate maintenance, inspection, and the like. However, when the organic solvent-based gas is detected by the gas sensor, a fluoride-based salt present in the electrolyte reacts with moisture to generate a fluoride-based gas such as highly corrosive Hydrogen Fluoride (HF), and therefore the gas sensor is also exposed to the fluoride-based gasAnd (3) a body. As described above, since the fluoride-based gas is a corrosive gas, there is a problem that the detection element of the gas sensor deteriorates and the detection performance deteriorates.
In addition, sulfur hexafluoride (SF)6) Electrical equipment such as gas transformers, gas circuit breakers, and gas insulated switchgear are used as insulators and arc extinguishing media. SF6Is very stable at normal temperature and pressure, but is thermally decomposed by non-cast steel or copper heated to 700-900 ℃ to generate sulfur tetrafluoride (SF)4)，SF4Reacts with a metal such as an alkali metal hydroxide to produce a metal sulfide and a fluoride such as highly corrosive HF. Does not react with water at normal temperature, but reacts with water at high temperature and high pressure to generate sulfuryl fluoride (SO) which is a toxic gas2F2) And the like. Furthermore, fluoride-based gases such as HF are also used in semiconductor manufacturing processes. Therefore, it is assumed that many situations of a fluoride-based gas exist in the use environment of the gas sensor.
Since a fluoride-based gas, which is a corrosive gas, imposes a burden on the environment, a gas sensor for monitoring the atmosphere so as not to release the fluoride-based gas into the environment has been reported (for example, see patent document 1). Patent document 1 discloses a technique of using hexafluoro-1, 3-butadiene (hereinafter, may be abbreviated as "C" in some cases) as a fluoride-based gas used as an etching gas or a cleaning gas in a semiconductor manufacturing process4F6") is contacted with a heated noble metal catalyst such as a palladium-based catalyst or a platinum-based catalyst, and is thermally decomposed and converted into HF, and this HF is detected by a detection element to detect C4F6. Thus, C which cannot be detected due to the problem of sensor sensitivity in the prior art can be used4F6Converted to HF for efficient detection. However, the technique of patent document 1 aims to detect C as a fluoride-based gas by detecting HF, which is a converted gas generated by thermal decomposition4F6. Therefore, there is still a need to construct a technique for suppressing deterioration of the detection element due to a corrosive gas such as a fluoride-based gas.
Patent document 1: japanese patent laid-open No. 2018-80949
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a gas sensor which can maintain detection performance without a detection element for detecting a gas to be detected contained in a gas to be measured being corroded by a fluoride-based gas even in an environment where the gas to be measured contains the fluoride-based gas which is a corrosive gas, can stably detect the gas to be detected with high accuracy over a long period of time, and has excellent durability.
Therefore, the present inventors have found that a fluoride-based gas contained in a gas to be measured can be adsorbed by an alkali hydroxide, a strongly basic anion exchange group, or the like, and that a member carrying the alkali hydroxide, the strongly basic anion exchange group, or the like can be mounted on a gas sensor, whereby the present invention can be suitably applied to detection of a gas to be detected in an environment in which the gas to be measured contains a fluoride-based gas that is a corrosive gas, and the detection performance can be stably maintained for a long period of time. The present inventors have also found that a gas to be detected can be converted into a substance having good sensitivity to a detection element by using an alkali hydroxide, a strongly basic anion exchange group, or the like, and that good gas detection sensitivity can be ensured by detecting the converted gas. The present inventors have completed the present invention based on these findings.
That is, the present invention relates to a gas sensor for detecting a specific detection target gas in a gas to be measured, the gas sensor including: a detection unit including a detection element for detecting the gas to be detected, and an adsorption conversion unit for adsorbing a fluoride-based gas contained in the gas to be measured on an upstream side of the detection unit in a gas passage through which the gas to be measured flows down the detection unit; the adsorption conversion part includes at least one selected from a hydroxide-based adsorption conversion material in which an alkali hydroxide is supported on an insoluble carrier, and an ion exchange-based adsorption conversion material in which a strongly basic anion exchange group is supported on an insoluble carrier.
According to this configuration, it is possible to provide a gas sensor in which a fluoride-based gas contained in a gas to be measured can be adsorbed by mounting an adsorption conversion section containing at least one selected from a hydroxide-based adsorption conversion material in which an alkali hydroxide is supported on an insoluble carrier and an ion exchange-based adsorption conversion material in which a strongly basic anion exchange group is supported on an insoluble carrier on the gas sensor, and thereby a detection section, particularly a detection element, can be protected from the fluoride-based gas. Since a fluoride-based gas is highly corrosive, the conventional gas sensor has a problem that the fluoride-based gas corrodes the detection element and the like when used in an environment in which the gas to be measured contains the fluoride-based gas, thereby deteriorating the long-term stability of the detection performance of the gas sensor. In contrast, the gas sensor of this configuration can be suitably used for detecting a gas to be detected in an environment in which a fluoride-based gas, which is a corrosive gas, is contained in a gas to be measured, has excellent durability, and can stably maintain detection performance for a long period of time.
In another feature, the adsorption/conversion section is provided with a hydroxide-based adsorption/conversion material and an ion exchange-based adsorption/conversion material in this order from the upstream side.
According to this configuration, since the hydroxide-based adsorption conversion material and the ion exchange-based adsorption conversion material are provided as the adsorption conversion unit in this order from the upstream side of the gas flow path through which the gas to be measured flows down toward the detection element, the fluoride-based gas that is not adsorbed by the hydroxide-based adsorption conversion material on the upstream side can be adsorbed by the ion exchange-based adsorption conversion material on the downstream side, and thus the detection element can be effectively protected from the fluoride-based gas. Therefore, the gas sensor having this configuration can maintain the detection performance more stably for a long period of time.
Further, the alkaline hydroxide is selected from manganese hydroxide (Mn (OH))2) Ferrous hydroxide (Fe (OH)2) Iron hydroxide (Fe (OH))3) Zinc hydroxide (Zn (OH)2) Copper hydroxide (Cu (OH)2) Aluminum hydroxide (Al (OH)3) Lanthanum hydroxide (La (OH)3) At least one of (a).
According to this configuration, since the compound having a basicity sufficient to adsorb the fluoride-based gas is used as the basic hydroxide, the detection unit, particularly the detection element, can be effectively protected from the fluoride-based gas. Further, since these alkaline hydroxides are hardly water-soluble and have low deliquescence, the hydroxide-based adsorption conversion material can be stabilized for a long period of time, and the adsorption performance of the fluoride-based gas can be maintained for a long period of time. Therefore, the gas sensor having this configuration can maintain the detection performance more stably for a long period of time.
Still another feature is that the strongly basic anion exchange group is a trimethylammonium group or a dimethylethanolammonium group.
According to this configuration, since the strongly basic anion exchange group having a basicity sufficient to adsorb the fluoride-based gas is used as the strongly basic anion exchange group, the detection section, particularly the detection element, can be effectively protected from the fluoride-based gas. Therefore, the gas sensor having this configuration can maintain the detection performance more stably for a long period of time.
In still another feature, the fluoride-based gas is hydrogen fluoride.
According to this configuration, the detection unit, particularly the detection element, can be effectively protected from hydrogen fluoride, which is a fluoride-based gas and has high corrosiveness. Therefore, the gas sensor having this configuration can maintain the detection performance more stably for a long period of time.
In still another feature, the adsorption conversion unit adsorbs the fluoride-based gas and decomposes the gas to be detected to generate a converted gas, and the detection unit includes a detection element that detects the generated converted gas.
According to this configuration, the adsorption conversion section, which is mounted on the gas sensor and contains at least one selected from the group consisting of a hydroxide-based adsorption conversion material in which an alkali hydroxide is supported on an insoluble carrier and an ion exchange-based adsorption conversion material in which a strongly basic anion exchange group is supported on an insoluble carrier, can adsorb not only a fluoride-based gas but also a gas to be detected into a substance having good sensitivity to a detection element, and by detecting the converted gas, good gas detection sensitivity can be ensured. In addition, by converting to a low molecular substance, the heating temperature for improving the reactivity can be set low, and low power consumption can be achieved. Further, since the adsorption of the fluoride-based gas and the conversion of the gas to be detected can be performed by one member, the structure of the gas sensor can be simplified. Conventionally, a technique has been used in which a gas to be detected is detected by detecting a converted gas generated by thermal decomposition in the presence of a noble metal catalyst or the like. On the other hand, according to the gas sensor having this configuration, the gas to be detected can be converted into a substance having good sensitivity to the detection element by using a basic substance such as an alkali hydroxide or a strongly basic anion exchange group, and thus, a catalyst or heating at a high temperature is not required, and the cost can be reduced.
In still another feature, the gas to be detected is a carbonate, the adsorption conversion unit adsorbs the fluoride-based gas and decomposes the carbonate to produce an alcohol, and the detection unit includes a detection element that detects the produced alcohol.
With this configuration, it is possible to provide a gas sensor capable of converting a carbonized ester as a gas to be detected into an alcohol which is a substance having good sensitivity to a detection element, and detecting the alcohol, thereby ensuring good gas detection sensitivity. According to the gas sensor having this configuration, for example, a failure and a sign of the failure such as LIB using carbonate as an organic solvent of an electrolyte can be detected. Therefore, the gas sensor having this configuration can provide a function of preventing a failure of LIB or the like, contributing to construction of a symptom detection technique such as appropriate maintenance and inspection, and the like, can be constructed as a symptom detection sensor, and can stably maintain detection performance for a long period of time.
Drawings
Fig. 1 is a schematic cross-sectional view showing a structure of an example of a gas sensor.
Fig. 2 is a perspective view showing a configuration of an example of a gas sensor, and shows an example of a configuration of a gas sensor including a housing.
Fig. 3 is a diagram summarizing a reaction mechanism of conversion of carbonate as an example of a gas to be detected by a gas sensor.
Fig. 4 is a flowchart schematically showing the operation of the gas sensor, and shows an example in which carbonate is used as the gas to be detected.
Description of the symbols:
1 … gas sensor;
10 … detection part;
11 … a detection element;
12 … a test element support substrate;
a 13 … terminal;
20 … adsorption conversion part;
21 … hydroxide-based adsorption conversion material;
21a … alkaline hydroxide;
21b … parent material;
22 … the ion exchange system adsorbs the conversion material;
23 … carrier support;
30 … adsorbing the conversion section support;
31 … air holes;
40 … a housing;
50 … gas inlet.
Detailed Description
Hereinafter, the gas sensor according to the embodiment of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below.
The gas sensor 1 of the present embodiment includes: a detection unit 10 including a detection element 11 for detecting a gas to be detected; and an adsorption conversion part 20 for protecting the detection part 10, particularly the detection element 11, from the influence of the fluoride-based gas. Since the fluoride-based gas has a very strong oxidizing action, it is highly corrosive. Therefore, when the fluoride-based gas comes into contact with the detection element 11 of the gas sensor 1, the detection element 11 is corroded, and the long-term stability of the detection performance of the gas sensor 1 is lowered. Therefore, the detection element 11 needs to be protected from the fluoride-based gas. The gas sensor 1 of the present embodiment is provided with the adsorption conversion portion 20 that adsorbs a fluoride-based gas to protect the detection element 11 from the fluoride-based gas, and thus the gas sensor 1 of the present embodiment can improve the durability against the fluoride-based gas and can improve the long-term stability of the detection performance.
Examples of the fluoride-based gas that causes the deterioration of the detection unit 10, particularly the detection element 11, include, but are not limited to, Hydrogen Fluoride (HF), sulfur fluoride, and carbon fluoride. As the sulfur fluoride, for example, disulfur difluoride (S) is mentioned2F2) Sulfur tetrafluoride (SF)4) Sulfur hexafluoride (SF)6) Dithiodecafluoride (S)2F10) And the like, but are not limited thereto. As the carbon fluoride, for example, carbon tetrafluoride (CF) is mentioned4) Hexafluoroethane (C)2F6) Octafluoropropane (C)3F8) Hexafluoro 1, 3 butadiene (C)4F6) Octafluorocyclobutane (C)4F8) Octafluorocyclopentene (C)5F8) And the like, but are not limited thereto. The fluoride-based gas exemplified here contains a gas species which is stable at normal temperature and pressure, has low corrosiveness, or has no corrosiveness, but may be decomposed into highly corrosive hydrogen fluoride or the like by thermal decomposition or the like, and thus, an example of the gas species which may cause deterioration of the detection element 11 is given.
The gas to be measured in the gas sensor 1 of the present embodiment may be any gas present in the environment as long as it contains the gas to be detected. The detection target gas is not limited as long as it can be detected by the detection element 11. Examples of the gas to be detected include, but are not limited to, flammable gases such as organic solvent gases including carbonate-based gases used as an electrolyte of a lithium ion battery, material gases for gas insulators, gas extinguishing medium liquid crystal applications, semiconductor applications, and the like, and toxic gases. Therefore, the gas sensor 1 of the present embodiment can be used for various applications such as safety applications for detecting flammable and toxic gases, vehicle-mounted applications for controlling and maintaining a lithium ion battery (hereinafter sometimes referred to as "LIB") mounted in a hybrid vehicle, an electric vehicle, or the like and a fuel cell mounted in a fuel cell vehicle, industrial applications for monitoring exhaust gas, such as combustion control and chemical reaction in an industrial production process, and environmental applications for monitoring air.
The gas sensor 1 of the present embodiment is explained based on the drawings. In the drawings, the same components are denoted by the same reference numerals, and detailed descriptions of the overlapping components are omitted.
Fig. 1 is a schematic cross-sectional view of a structure of an example of a gas sensor 1 according to the present embodiment. As shown in fig. 1, a gas sensor 1 of the present embodiment includes: a detection unit 10 for detecting a gas to be detected; and an adsorption conversion part 20, the adsorption conversion part 20 adsorbing the fluoride-based gas to protect the detection part 10 from the fluoride-based gas.
The detection unit 10 includes a detection element 11 sensitive to a detection target gas. The detection element 11 may be disposed on a detection element support base 12 made of an appropriate substrate or the like. The gas sensor 1 of the present embodiment may be configured to detect the detection target gas through the converted gas generated by converting the detection target gas, and in this case, the detection element 11 may be configured to be sensitive to the converted gas.
The type of the detection element 11 is appropriately selected according to the type of the gas sensor 1, the type of the detection target gas, and the like. The gas sensor 1 of the present embodiment may be constructed as a gas sensor 1 based on a known detection principle, such as a semiconductor type gas sensor, a catalytic combustion type gas sensor, a heat conduction type gas sensor, or an electrochemical type sensor.
When the gas sensor 1 of the present embodiment is a semiconductor type gas sensor, the detection element 11 may be formed of, for example, tin oxide (SnO) formed on a heating coil and a carrier such as alumina2) Indium (III) oxide (In)2O3) And metal oxide semiconductors such as zinc oxide (ZnO). When the gas sensor 1 of the present embodiment is configured as a catalytic combustion gas sensor, the detection element 11 may be a noble metal coil such as platinum, for exampleThe surface of the detection element (2) is covered with a carrier such as alumina carrying a catalyst made of noble metal such as platinum or palladium which is active with respect to the gas to be detected, and as the compensation element, for example, a compensation element obtained by sintering a mixture of alumina and glass inert with respect to the gas to be detected on a coil of noble metal such as platinum or the like can be used. When the gas sensor 1 of the present embodiment is configured as a heat conduction gas sensor, the detection element 11 and the compensation element may be formed of, for example, an element obtained by sintering a mixture of alumina and glass, which is inert to the gas to be detected, on a noble metal coil such as platinum, or an element coated with an inert metal or the like, and the compensation element has a sealed structure that does not contact the gas to be detected. When the gas sensor 1 of the present embodiment is an electrochemical sensor, the gas sensor may be configured as a solid electrolyte gas sensor using ion conductivity of a solid electrolyte, and, for example, zirconium oxide (ZrO) may be used as the detection element 112) Calcium oxide (CaO) and yttrium oxide (Y) are added as main constituent materials2O3) And the stabilized zirconia obtained thereby.
The detection element 11 is preferably designed as a solid body. The gas sensor 1 in which the detection element 11 is a solid is referred to as a solid-state gas sensor, and corresponds to the semiconductor gas sensor, the catalytic combustion gas sensor, the heat conduction gas sensor, the electrochemical sensor using a solid electrolyte, and the like. The solid-state gas sensor can also be suitably used as an on-vehicle gas sensor exposed to high and low temperatures. In general, a solid-state gas sensor is more likely to cause deterioration of the detection element 11 due to a corrosive gas such as a fluoride-based gas than an electrochemical gas sensor using an electrolyte solution or the like. However, by applying the configuration of the gas sensor 1 of the present embodiment to a solid-state gas sensor, it is possible to suppress deterioration of the detection element 11 due to a corrosive gas such as a fluoride-based gas, as compared with a conventional solid-state gas sensor.
In fig. 1, the adsorption conversion section 20 is disposed on the upper layer of the detection section 10. In fig. 1, the gas to be measured flows downward from above, and the adsorption conversion unit 20 is disposed upstream of the detection unit 10 in the gas flow path in which the gas to be measured flows downward toward the detection unit 10. With this configuration, the gas to be measured passes through the adsorption conversion unit 20 and then reaches the detection unit 10. Therefore, the fluorine-based gas contained in the gas to be measured is removed by the adsorption conversion unit 20 in the process in which the gas to be measured flows down the detection unit 10, and therefore, the detection unit 10 can be prevented from being exposed to the fluorine-based gas. This can reduce corrosion of the detection unit 10, particularly the detection element 11, by the fluoride-based gas, and improve the durability of the gas sensor 1 of the present embodiment against the fluoride-based gas, thereby improving the long-term stability of the detection performance.
The adsorption conversion part 20 is configured to contain at least one selected from a hydroxide-based adsorption conversion material 21 in which an alkali hydroxide is supported on an insoluble carrier, and an ion exchange-based adsorption conversion material 22 in which a strongly basic anion exchange group is supported on an insoluble carrier. The thickness, size, and the like of the adsorption conversion section 20 are not particularly limited, and may be appropriately set according to the type and size of the detection element 11 of the gas sensor 1, the type of the gas to be measured, the content of the fluoride-based gas, the size of the flow channel in which the adsorption conversion section 20 is provided, and the like.
The hydroxide-based adsorption conversion material 21 may be a material in which the alkali hydroxide 21a is supported on an appropriate insoluble carrier by physical adsorption or the like, and as the carrier, a porous carrier or the like can be preferably used.
The porous carrier is not particularly limited as long as it has a three-dimensional pore structure that allows gas to pass through and has a plurality of minute pores formed therein, the pores being capable of supporting the alkaline hydroxide 21 a. Therefore, the basic hydroxide 21a can be supported in the porous carrier, and the pore diameter, the pore ratio, the pore distribution, and the like of the porous carrier can be appropriately set, and the shape of the pores is not limited, and may be continuous pores in which pores are continuous, or may be independent pores in which pores are not continuous. Examples of the porous support include porous woven fabric materials, nonwoven fabric (felt) materials, sponge materials, and fiber materials. Examples of the material include, but are not limited to, synthetic resin materials such as polyethylene, polypropylene, and polyurethane, carbon materials, metal alloy materials such as stainless steel, aluminum, titanium, and nickel, and metal oxide materials such as silica and alumina. As shown in fig. 1, a coarse multilayer structure formed by laminating woven or nonwoven fabrics of the above-described synthetic resin material, carbon material, metal/alloy material, metal oxide material, or the like, and the like, is also included in the porous carrier, and the alkali hydroxide 21a is fixed to the matrix material 21b of the fiber material by physical adsorption or the like. The porous carrier may be used alone or in combination of two or more.
The alkaline hydroxide 21a is a hydroxide represented by the general formula M (OH) n (M is a metal element, and n is the valence of the metal element M), and is preferably a poorly water-soluble alkaline hydroxide. Here, the sparingly water-soluble substance means an insoluble substance hardly soluble in water or substantially insoluble in water. From the viewpoint of long-term stability of the fluoride-based gas adsorption performance, the alkali hydroxide 21a is preferably not only poorly water-soluble but also low in deliquescence. For example, examples of M include lithium, sodium, potassium, manganese (II), iron (III), zinc, copper (II), aluminum, lanthanum (III), and cobalt (II). Specifically, the hydroxide includes manganese hydroxide (Mn (OH)2) Ferrous hydroxide (Fe (OH)2) Iron hydroxide (Fe (OH))3) Zinc hydroxide (Zn (OH)2) Copper hydroxide (Cu (OH)2) Aluminum hydroxide (Al (OH)3) Lanthanum hydroxide (La (OH)3) Cobalt (II) hydroxide (Co (OH)2) And the like, but are not limited thereto. The alkali hydroxide 21a may be used alone or in combination of two or more.
In the hydroxide-based adsorption conversion material 21, the alkaline hydroxide 21a carried in the insoluble carrier reacts with fluorine, which is a constituent component of the fluoride-based gas, to trap fluorine. That is, the metal which is a constituent component of the alkali hydroxide 21a reacts with fluorine of the fluoride-based gas to form a fluoride-based salt (MF)n: n is the valence of the metal element M). The fluoride-based salt thus formed is supported on an insoluble carrier, whereby a fluoride-based gas is adsorbed inside the hydroxide-based adsorption conversion material 21.
The following shows typical examples of the reaction between the alkali hydroxide 21a and the fluoride-based gas, but the reaction is not limited to these.
(A) Reaction with alkaline hydroxide 21a
(1) Reaction with hydrogen fluoride
M(OH)n+nHF→MFn+nH2O
(wherein M is a hydroxyl group and a salt, preferably a metal element forming a salt which is hardly soluble in water, for example, lithium, sodium, potassium, manganese (II), iron (III), zinc, copper (II), aluminum, lanthanum (III), cobalt (II) or the like, any M represents the same metal element, n is the valence of the metal element M, and any n represents the same number.)
(2) Reaction with sulfur fluoride
(2-1) Difluorinated disulfide (S)2F2)
2S2F2+6MOH→M2SO3+3S+4MF+3H2O
(wherein M is a hydroxyl group or a salt, preferably a monovalent metal element forming a salt which is hardly soluble in water, for example, lithium, sodium, potassium or the like, and any M represents the same metal element)
2S2F2+3M(OH)2→MSO3+3S+2MF2+3H2O
(wherein M represents a hydroxyl group or a salt, preferably a divalent metal element forming a salt which is hardly soluble in water, for example, manganese (II), iron (II), zinc, copper (II), cobalt (II) or the like, and any M represents the same metal element.)
6S2F2+6M(OH)3→M2(SO3)3+9S+4MF3+9H2O
(wherein M represents a hydroxyl group or a salt, preferably a trivalent metal element which forms a salt hardly soluble in water, for example, iron (III), aluminum, lanthanum (III), etc., and any M represents the same metal element.)
(2-2) Sulfur tetrafluoride (SF)4)
SF4+6MOH→M2SO3+4MF+3H2O
(wherein M represents a hydroxyl group or a salt, preferably a monovalent metal element forming a salt which is hardly soluble in water, and the above-mentioned elements are exemplified, and any M represents the same metal element)
SF4+3M(OH)2→MSO3+2MF2+3H2O
(wherein M represents a hydroxyl group or a salt, preferably a divalent metal element forming a salt which is hardly soluble in water, and the elements are exemplified, and any M represents the same metal element)
SF4+6M(OH)3→M2(SO3)3+4MF2+9H2O
(wherein M represents a hydroxyl group or a salt, preferably a trivalent metal element forming a salt which is hardly soluble in water, and the above-mentioned elements are exemplified, and any M represents the same metal element)
(2-3) Gedecafluorodithio (S)2F10)
S2F10+14MOH→M2SO3+M2SO4+10MF+7H2O
(wherein M represents a hydroxyl group or a salt, preferably a monovalent metal element forming a salt which is hardly soluble in water, and the above-mentioned elements are exemplified, and any M represents the same metal element)
S2F10+7M(OH)2→MSO3+MSO4+5MF2+7H2O
(wherein M represents a hydroxyl group or a salt, preferably a divalent metal element forming a salt which is hardly soluble in water, and the elements are exemplified, and any M represents the same metal element)
3S2F10+14M(OH)3→M2(SO3)3+M2(SO3)4+10MF2+21H2O
(wherein M represents a hydroxyl group or a salt, preferably a trivalent metal element forming a salt which is hardly soluble in water, and the above-mentioned elements are exemplified, and any M represents the same metal element)
The ion exchange adsorption conversion material 22 may be a material in which strongly basic anion exchange groups are supported on an appropriate insoluble carrier. As the insoluble carrier, a polymer compound or the like can be preferably used. Therefore, the ion exchange resin in which the strongly basic anion exchange groups are introduced into the matrix material can be configured in a form in which the strongly basic anion exchange groups are introduced into the three-dimensional network structure of the molecular chains of the polymer compound. The polymer compound constituting the ion exchange resin is not particularly limited as long as it can introduce strongly basic anion exchange groups into its molecular structure. Specifically, synthetic resins such as styrene, acrylic, and methacrylic resins can be used, and copolymers containing Divinylbenzene (DVB) polyfunctional monomers and the like as crosslinking agents can also be prepared. The ion exchange resin may be of a gel type or a porous type, and the shape thereof is not particularly limited, and may be in the form of beads or the like. Further, the ion exchange resin may be further supported in the porous carrier as described above.
Preferably, the strongly basic anion exchange group is a quaternary ammonium group. Therefore, the anion exchange resin may be a strongly basic anion exchange resin of type I having a trimethylammonium group, a strongly basic anion exchange resin of type II having a dimethylethanolaminium group, or a combination of both. The structures of strongly basic anion exchange resins of type I and type II (ion exchange resin of Mitsubishi chemical, resin for separation and purification, DIAION) are shown belowTM SEPABEADSTM MCI GELTMIntroduction of commercial product > ion exchange resin > strongly basic anion exchange resin, Internet, 5 months in 2019 and 10 days in retrieval<URL：https://www.diaion.com/products/ion_03_01.html)。
In the ion exchange adsorption conversion material 22, the strongly basic anion exchange groups carried on the insoluble carrier in the same manner as in the hydroxide adsorption conversion material 21 react with fluorine, which is a constituent component of the fluoride-based gas, to capture fluorine. For example, the strongly basic anion exchange groups introduced into the three-dimensional structure in the form of a mesh of the molecular chains of a polymer, which is a matrix material such as an ion exchange resin, capture fluorine, and the fluorine is fixed inside the three-dimensional structure of the molecular chains of the polymer, thereby adsorbing the fluoride-based gas to the ion exchange adsorption conversion material 21.
Typical examples of the reaction between the strongly basic anion exchange group and the fluoride-based gas are shown below, but the reaction is not limited to these. Thus, although the following examples show examples using trimethylammonium groups (type I) as strongly basic anion exchange groups, the same reaction proceeds with dimethylethanolaminium groups (type II).
(B) Reaction with strongly basic anion exchange groups
(1) Reaction with hydrogen fluoride
R-[N(CH3)3]+[OH]-+HF→R-N(CH3)3F+H2O
(wherein R represents a molecular chain of a polymer such as a styrene polymer or an acrylic polymer which is a matrix material of an ion exchange resin.)
(2) Reaction with sulfur fluoride
(2-1) Difluorinated disulfide (S)2F2)
2S2F2+6(R-[N(CH3)3]+[OH]-)→(R-N(CH3)3)2SO3+3S+4(R-N(CH3)3)F+3H2O
(wherein R represents a molecular chain of a polymer such as a styrene polymer or an acrylic polymer which is a matrix material of an ion exchange resin.)
(2-2) Sulfur tetrafluoride (SF)4)
SF4+6(R-[N(CH3)3]+[OH]-)→(R-N(CH3)3)2SO3+4((R-N(CH3)3)F)+3H2O
(wherein R represents a molecular chain of a polymer such as a styrene polymer or an acrylic polymer which is a matrix material of an ion exchange resin.)
Fig. 1 shows an example in which the adsorption/conversion unit 20 is composed of a hydroxide-based adsorption/conversion material 21 and an ion exchange-based adsorption/conversion material 22, and the hydroxide-based adsorption/conversion material 21 and the ion exchange-based adsorption/conversion material 22 are arranged and laminated from the upstream side of the gas flow path through which the gas to be measured flows down the detection unit 10 including the detection element 11. Thus, the fluoride-based gas that is not adsorbed by the hydroxide-based adsorption conversion material 21 can be adsorbed by the ion exchange-based adsorption conversion material 22, and the detection unit 10, particularly the detection element 11, can be effectively protected from the fluoride-based gas. However, the ion exchange adsorption conversion material 22 may be disposed and laminated on the upstream side. Further, in the case where the hydroxide-based adsorbing conversion material 21 is disposed further on the downstream side, or in the case where a plurality of hydroxide-based adsorbing conversion materials 21 and ion exchange-based adsorbing conversion materials 22 are stacked, the order of stacking, the number of stacking, and the like may be unlimited. Alternatively, the hydrogen oxide adsorption conversion material 21 and the ion exchange adsorption conversion material 22 may be independently formed.
As shown in fig. 1, a support 23 may be provided in the adsorption conversion section 20, and a surface of the support 23 opposite to the detection section 10 may be laminated so as to be covered with an ion exchange adsorption conversion material 22 such as an ion exchange resin in a bead form. This makes it possible to support and fix the ion exchange adsorption conversion material 22 and also the alkaline hydroxide-based adsorption conversion material 21 disposed on the upstream side thereof.
The support 23 needs to have a strength capable of supporting the ion exchange adsorptive conversion substance 22 and the hydroxide adsorptive conversion substance 21. The support 23 has a function as a separator, that is, a function of preventing a carrier such as the alkaline hydroxide 21a of the alkaline hydroxide-based adsorption conversion material 21 and the ion exchange resin constituting the ion exchange adsorption conversion material 22 from flowing down toward the detection unit 10, and has a permeability capable of transmitting the gas to be detected. Therefore, the carrier support 23 is not particularly limited as long as it is not permeable to the carrier but permeable to the gas to be detected and has a strength capable of supporting the ion-exchange adsorptive conversion material 22 and the hydroxide-based adsorptive conversion material 21, and may be made of a known material and have any size and shape. For example, the material may be a synthetic resin material, a metal alloy material, a metal oxide material, a carbon material, or the like. The mesh member is preferably a woven fabric formed by weaving fine wires of a metal material such as stainless steel, a metal mesh formed by punching a metal or the like, a resin mesh formed by weaving fine wires of a synthetic resin material such as polyester, or the like.
The adsorption conversion part support 30 may be disposed between the detection part 10 and the adsorption conversion part 20, and may be configured to support the adsorption conversion part 20. The adsorption conversion section 20 is disposed on the surface of the adsorption conversion section support 30 opposite to the detection section 10. The adsorption conversion part support 30 may further have a function of separating the adsorption conversion part 20 from the detection part 10. The adsorption conversion part support 30 may be disposed separately from the detection part 10, thereby forming a space for gas diffusion between the detection part 10 and the adsorption conversion part 20.
The adsorption conversion part support 30 is not particularly limited as long as it is permeable to the detection target gas and has a strength capable of supporting the adsorption conversion part 20, and a known material can be used, and it may have any size and shape. For example, the gas permeable member may be made of a synthetic resin material, a carbon material, a metal alloy material, or a metal oxide material, and may have a structure in which gas permeable holes 31 having a predetermined pore diameter are formed. The diameter, shape, number, and the like of the air holes 31 formed in the adsorption conversion section support 30 are not particularly limited as long as the gas to be detected can pass through them. The adsorption conversion section support 30 is preferably formed of the above-mentioned metal material such as stainless steel, and can be configured as a reversed cup-shaped member that is opened downward, and the ventilation holes 31 are formed in the upper surface (bottom surface of the cup). The adsorption conversion portion support 30 configured as an inverted cup-shaped member may be arranged to cover the detection element 11.
The gas sensor 1 of the present embodiment may have a configuration in which the detection unit 10 and the adsorption conversion unit 20 are disposed in the housing 40 as shown in fig. 2. The shape, size, material, and the like of the case 40 are not limited, and may be, for example, a columnar shape, a cubic shape, a prismatic shape such as a rectangular parallelepiped, or the like.
As shown in fig. 2, the gas sensor 1 of the present embodiment includes a case 40 having a gas inlet 50 for introducing a gas to be measured, and a detection unit 10 and an adsorption conversion unit 20 which are arranged in the case from a lower layer. Specifically, at least one selected from the group consisting of the detection element support base 12 (connected to the terminal 13) as a constituent element of the detection section 10, the detection element 11, the adsorption conversion section support 30, the carrier support 23 as a constituent element of the adsorption conversion section 20, and the hydroxide-based adsorption conversion material 21 and the ion exchange-based adsorption conversion material 22 is arranged in this order from the lower layer. The upper surface of the adsorption conversion part 20 may be disposed so as to be exposed to the gas inlet 50 of the casing 40.
The gas sensor 1 of the present embodiment is constructed in such a manner that the gas to be measured is naturally diffused and introduced into the case 40 through the gas introduction port 50, using the difference in gas concentration between the outside of the case 40 and the inside of the case 40 as the driving force. Further, a pressurizing mechanism or the like may be provided to forcibly introduce the gas to be measured into the case 40.
The operation of the gas sensor 1 of the present embodiment will be described. In the gas sensor 1 of the present embodiment, the adsorption converter 20 adsorbs the fluoride-based gas contained in the gas to be measured while the gas to be measured introduced from the gas introduction port 50 or the like flows down to the detector 10 through the adsorption converter 20. The gas to be measured flowing down to the detection unit 10 contains no or a very small amount of a fluoride-based gas, and thus the detection unit 10, particularly the detection element 11, can be effectively protected from the fluoride-based gas, which is a corrosive gas.
According to the gas sensor 1 of the present embodiment, the adsorption conversion part 20 on which at least one selected from the hydroxide-based adsorption conversion material 21 in which the basic hydroxide 21a is supported on the insoluble carrier and the ion exchange-based adsorption conversion material 22 in which the strongly basic anion exchange group is supported on the insoluble carrier is provided, so that the fluoride-based gas contained in the gas to be measured can be adsorbed, and the detection part 10, particularly the detection element 11, can be protected from the fluoride-based gas. Since the fluoride-based gas is highly corrosive, the conventional gas sensor has a problem that the fluoride-based gas corrodes the detection element and the like to deteriorate the long-term stability of the detection performance of the gas sensor 1 when used in an environment in which the gas to be measured contains the fluoride-based gas. In contrast, the gas sensor 1 of the present embodiment can be suitably applied to detection of a gas to be detected in an environment in which a fluoride-based gas, which is a corrosive gas, is contained in a gas to be measured, has excellent durability, and can stably maintain detection performance for a long period of time.
(other embodiments)
The gas sensor 1 of the present embodiment can be configured to convert a gas to be detected into a converted gas having good sensitivity of the detection element 11. Here, the conversion is generally explained as a technique of "detecting a detection target gas by detecting a converted gas generated by thermal decomposition", but here, it is explained as including decomposition by an alkaline substance as in the gas sensor 1 of the present embodiment.
In the gas sensor 1 of the present embodiment, the detection element 11 in the detection portion 10 is configured to have sensitivity to the conversion gas. The conversion of the detection target gas into the converted gas may be performed by the adsorption conversion unit 20.
As the detection target gas in the gas sensor 1 of the present embodiment, a carbonate-based gas, an alcohol-based gas, or the like can be preferably exemplified. In the following, an embodiment in which the detection target gas is composed of a carbonate-based gas will be described with respect to the gas sensor 1 of the present embodiment, but the gas sensor can be similarly configured in the case where other types of gases are used as the detection target gas.
Here, the carbonate suitable as the gas to be detected is an organic solvent widely used as an electrolyte of LIB, a solvent, a fuel additive, a raw material of an agricultural chemical or a pharmaceutical, etc., and has a structure in which CO (OH) is substituted with a hydrocarbon group2And (3) at least one of 2 hydrogen atoms. The carbonate may be a chain carbonate, a cyclic carbonate, or a carbon of a hydrocarbon groupThe number of atoms is also not particularly limited. The hydrocarbon group may have a substituent such as a halogen atom, e.g., a fluorine atom. Examples of the carbonate include ethyl carbonate (hereinafter, sometimes referred to as "EC"), diethyl carbonate (hereinafter, sometimes referred to as "DEC"), propylene carbonate (hereinafter, sometimes referred to as "PC"), dimethyl carbonate (hereinafter, sometimes referred to as "DMC"), ethyl methyl carbonate (hereinafter, sometimes referred to as "EMC"), fluoroethylene carbonate (hereinafter, sometimes referred to as "FEC") ·. In the electrolyte solution of LIB, a mixed solution of cyclic carbonate and chain carbonate in which LiPF is dissolved is used6、LiBF4Since carbonates such as electrolyte salts have high volatility, detection of carbonate-based gases is useful for controlling and maintaining LIB.
Therefore, in the gas sensor 1 of the present embodiment, the carbonate-based gas as the gas to be detected may be converted into alcohol, and the alcohol converted from carbonate may be detected by the detection unit 10 including the detection element 11. The detection element 11 can therefore be designed as an alcohol-sensitive element. The conversion of the carbonate gas can be performed by the adsorption conversion unit 20, and the adsorption conversion unit 20 adsorbs the fluoride-based gas to convert the carbonate gas.
Fig. 3 shows a reaction formula of a typical example of the conversion reaction of a carbonate to an alcohol. Fig. 3 shows an example of the reaction of converting carbonate by adsorbing the conversion material 21 with a hydroxide, but the same reaction is also performed by adsorbing the conversion material 22 with an ion exchange system. Further, fig. 3 shows an example in which a monovalent metal hydroxide is used as the alkali hydroxide constituting the hydroxide-based adsorption conversion material, but the same reaction is carried out using divalent and trivalent metal hydroxides.
In fig. 3, diethyl carbonate (DEC) is converted to carbonate and ethanol. Ethyl Carbonate (EC) is converted to carbonate and ethylene glycol. Propylene Carbonate (PC) is converted to carbonate and propylene glycol. Dimethyl carbonate (DMC) is converted into carbonate and methanol. Ethyl Methyl Carbonate (EMC) is converted to carbonate and methanol, ethanol. Since the converted alcohol has a lower boiling point than the carbonate, the converted alcohol is also a gas in an environment where the carbonate to be detected exists as a gas, and the carbonate can be detected by detecting the alcohol gas by the detection unit 10. In addition, a part or all of the carbonate may be further converted into carbon dioxide and an oxide.
The operation of the gas sensor 1 according to the present embodiment will be described with reference to fig. 4. Although fig. 4 shows an example in which the detection target gas is a carbonate-based gas, the same configuration is used when the detection target gas is another type of gas. Fig. 4 is a flowchart showing the operation of the gas sensor 1 in which a gas containing a fluoride-based gas as a corrosive gas in addition to a carbonate-based gas as a gas to be detected and HF is used as a gas to be measured, and as shown in fig. 1, an alkaline hydroxide-based adsorption conversion material 21 is disposed on the upstream side and an ion exchange-based adsorption conversion material 22 is disposed on the downstream side as an adsorption conversion section 20. In the gas flow path where the gas to be measured containing the carbonate-based gas and HF flows down inside the gas sensor 1, HF is adsorbed by the alkaline hydroxide-based adsorption conversion material 21, and the carbonate is converted into the alcohol and the carbonate. Some or all of the carbonate may also be further converted to carbon dioxide and oxides. The produced carbonate (which may contain converted carbon dioxide or oxide) is adsorbed on the basic hydroxide-based adsorption conversion material 21, while the alcohol passes through the basic hydroxide-based adsorption conversion material 21 in the form of gas toward the downstream side. Next, the gas flows down the ion exchange adsorption conversion material 22, and HF not adsorbed by the alkaline hydroxide adsorption conversion material 21 is adsorbed by the ion exchange adsorption conversion material 22, and the carbonate-based gas not subjected to the conversion is also subjected to the conversion to be converted into alcohol and carbonate. Some or all of the carbonate may also be further converted to carbon dioxide and oxides. The produced carbonate (which may contain carbon dioxide or oxide to be converted) is adsorbed on the ion exchange system adsorption conversion material 22. The alcohol is in contact with the detection unit 10 in the form of a gas, and the alcohol is detected by the detection element 11 of the detection unit 10, and the carbonate ester as the detection target gas is detected through the detection of the alcohol.
According to the gas sensor 1 of the present embodiment, the adsorption conversion part 20 mounted on the gas sensor 1 and including at least one selected from the hydroxide-based adsorption conversion material 21 in which the alkali hydroxide 21a is supported on the insoluble carrier and the ion-exchange-based adsorption conversion material 22 in which the strongly basic anion exchange group is supported on the insoluble carrier can convert a gas to be detected, such as a carbonate-based gas, into a substance having good sensitivity to the detection element 11 as well as adsorb a fluoride-based gas, and by detecting the converted gas, good gas detection sensitivity can be ensured. In addition, by converting to a low molecular substance, the heating temperature for improving the reactivity can be set low, and low power consumption can be achieved. Further, since the adsorption of the fluoride-based gas and the conversion of the gas to be detected can be performed by one member, the structure of the gas sensor 1 can be simplified. Conventionally, a technique has been used in which a gas to be detected is detected by detecting a converted gas generated by thermal decomposition in the presence of a noble metal catalyst or the like. On the other hand, according to the gas sensor 1 of the present embodiment, the gas to be detected can be converted into a substance having good sensitivity to the detection element 11 by using a basic substance such as the alkali hydroxide 21a or the strongly basic anion exchange group, and a catalyst or heating at a high temperature is not required, so that the cost can be reduced.
The gas sensor 1 of the present embodiment can be configured such that the gas to be detected is a carbonate ester, and for example, a failure or a sign of failure such as LIB using the carbonate ester as an organic solvent of an electrolyte can be detected. Therefore, the gas sensor 1 of the present embodiment can provide a function of being able to prevent a failure such as LIB, and being able to contribute to the construction of a symptom detection technique such as appropriate maintenance and inspection, and being able to be constructed as a symptom detection sensor, and being able to maintain the detection performance stably for a long period of time.
Industrial applicability
The present invention can be suitably applied to a gas sensor for detecting a gas to be detected in an environment in which a gas to be detected contains a fluoride-based gas that is a corrosive gas.
Claims (7)
1. A gas sensor for detecting a specific detection target gas among gases to be measured, comprising:
a detection section including a detection element for detecting the gas to be detected, and
an adsorption conversion unit that adsorbs a fluoride-based gas contained in the measurement target gas on an upstream side of the detection unit in a gas flow path in which the measurement target gas flows down the detection unit;
the adsorption conversion part comprises at least one selected from a hydroxide-based adsorption conversion material in which an alkali hydroxide is supported on an insoluble carrier, and an ion exchange-based adsorption conversion material in which a strongly basic anion exchange group is supported on an insoluble carrier.
2. The gas sensor according to claim 1, wherein the adsorption conversion section is provided with a hydroxide-based adsorption conversion material and an ion exchange-based adsorption conversion material in this order from the upstream side.
3. Gas sensor according to claim 1 or 2, wherein the alkaline hydroxide is selected from manganese hydroxides Mn (OH)2Ferrous hydroxide Fe (OH)2Fe (OH) iron hydroxide3Zinc hydroxide Zn (OH)2Copper hydroxide Cu (OH)2Aluminum hydroxide Al (OH)3Lanthanum hydroxide La (OH)3At least one of (a).
4. A gas sensor according to any one of claims 1 to 3, wherein the strongly basic anion exchange group is a trimethylammonium group or a dimethylethanolammonium group.
5. The gas sensor according to any one of claims 1 to 4, wherein the fluoride-based gas is hydrogen fluoride.
6. The gas sensor according to any one of claims 1 to 5, wherein the adsorption/conversion unit adsorbs the fluoride-based gas and decomposes the detection target gas to generate a converted gas, and the detection unit includes a detection element that detects the generated converted gas.
7. The gas sensor according to claim 6, wherein the gas to be detected is a carbonate ester, the adsorption conversion portion adsorbs the fluoride-based gas and decomposes the carbonate ester to generate an alcohol, and the detection portion includes a detection element that detects the generated alcohol.
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| CN113155913A (en) * | 2021-04-21 | 2021-07-23 | 浙江大学 | Gas sensor for detecting sulfur hexafluoride decomposition product and preparation method thereof |
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